Quaternary cationic polymers

ABSTRACT

A cationic polymer salt composition is provided that includes a reaction product derived from reaction of a polyamine or a polyalkyleneimine and a substituted alkyl trialkyl quaternary ammonium salt. Also provided are surfactant compositions. The compositions may also include carriers, such as water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, monoethyleneglycol, an ethyleneglycol monobutyl ether, and hexylene glycol.

FIELD OF THE INVENTION

This disclosure generally relates to cationic polymer salts, and moreparticularly to compositions to be used as surfactants, antimicrobialcompounds, and corrosion inhibitors.

BACKGROUND

Quaternary ammonium compounds comprise an important subcategory ofsurfactants because they contain unique properties. A main distinctionbetween quaternary ammonium compounds and other surfactants is theirunique structure. Quaternary ammonium compounds consist mainly of twomoieties, a hydrophobic group, e.g., long alkyl group, and a quaternaryammonium salt group. The unique positive charge of the ammonium plays akey role, i.e., electrostatic interactions, between the surfactant andsurface.

Industrial water systems employ process water to serve many differentpurposes but may be prone to microbial contamination and fouling.Fouling or deposition of any organic or inorganic material can occureven in industrial water systems treated with the best water treatmentprograms currently available.

If these industrial water systems are not periodically cleaned, thenthey will become heavily fouled. Fouling has a negative impact on theindustrial water system. For example, severe mineral scale (inorganicmaterial) will buildup on the water contact surfaces and anywhere thereis scale providing an ideal environment for microorganism growth.

Evaporative cooling water systems are particularly prone to fouling.This fouling occurs by a variety of mechanisms including deposition ofair-borne, water-borne, or water-formed contaminants; water stagnation;process leaks; and other factors. If allowed to progress, the system cansuffer from decreased operational efficiency, premature equipmentfailure, and increased health-related risks associated with microbialfouling.

Fouling can also occur due to microbiological contamination. Sources ofmicrobial contamination in industrial water systems are numerous and mayinclude, but are not limited to, air-borne contamination, water make-up,process leaks and improperly cleaned equipment. These microorganisms canestablish microbial communities on any wettable or semi-wettable surfaceof the water system.

Exopolymeric substances secreted by microorganisms aid in the formationof biofilms as the microbial communities develop on surfaces. Thesebiofilms are complex ecosystems that establish a means for concentratingnutrients and offer protection for growth, and biofilms can acceleratescale, corrosion, and other fouling processes. Not only do biofilmscontribute to reduction of system efficiencies, but they also provide anexcellent environment for microbial proliferation that can includeLegionella bacteria. It is therefore important that biofilms and otherfouling processes be reduced to the greatest extent possible to minimizethe health-related risk associated with Legionella and other water-bornepathogens.

Corrosion inhibitors are often added into upstream oil and gasproduction fluids to protect carbon steel pipelines and infrastructurefrom corrosion. Quaternary ammonium compounds have been used for manyyears as part of corrosion inhibitor formulations but are most often arebis quaternary species or species quaternized with benzyl chloride,which is known to be very hazardous.

There is a continuing need for quaternary ammonium compounds that fillthis niche of surfactants and corrosion inhibitors.

BRIEF SUMMARY

In some embodiments, a cationic polymer salt is provided which comprisesa reaction product derived from a reaction of a polyamine or apolyalkyleneimine and a substituted alkyl trialkyl quaternary ammoniumsalt.

In certain embodiments, the present disclosure provides a cationicpolymer salt comprising a reaction product derived from a reaction of apolyamine or a polyalkyleneimine and a substituted alkyl trialkylquaternary ammonium salt of formula (I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl.

In some embodiments, a cationic polymer salt is provided which comprisesformula (III):

wherein each R₆ is independently C₂-C₆ alkylene; each R₇ isindependently hydrogen, —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or—R₆—N—(R₆—N(R₈)₂)₂; each R₈ is independently hydrogen or

each R₉ is independently C₂-C₆ alkylene substituted with hydroxyl or—OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; R₁₃ is C₁-C₆ alkyl; n is an integer from 1 to 100; and eachX⁻ is independently an anion.

In some embodiments, a cationic polymer salt is provided which comprisesa reaction product derived from a reaction of a polyamine, analkyleneimine, or a polyalkyleneimine and a substituted alkyl trialkylquaternary ammonium salt of formula (I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with a hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl; and

wherein any one of the following:

(A) the cationic polymer salt has no substitutions within its mainchain, no alkyl-quaternized ammonium within its main chain, andcomprises at least 4 quaternary ammonium groups; or

(B) the cationic polymer salt has one or more terminal tertiary aminegroups having the formula (IV):

wherein R₁₁ is R₁ without the X⁻ end group, and either: the polymer salthas no substitutions within its main chain or at least 1 of R₂, R₃, andR₄ is a C₉-C₂₂ alkyl group; or

(C) R₂ and R₃ are C₆-C₂₂ alkyl or C₇-C₂₂ arylalkyl and R₄ is methyl.

In some embodiments, a method for controlling microbes in an aqueoussystem is disclosed. The method can include adding to the aqueous systema reaction product derived from a reaction of a polyamine or apolyalkyleneimine and a substituted alkyl trialkyl quaternary ammoniumsalt of formula (I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with a hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl.

In some embodiments of the present disclosure, a method is disclosed forcontrolling microbes in process water by adding a composition to theprocess water. The composition may include a cationic polymer of formula(III):

where each R₆ may be independently C₂-C₆ alkylene; each R₇ may beindependently hydrogen, —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or—R₆—N—(R₆—N(R₈)₂)₂; each R₈ may be independently hydrogen or

each R₉ may be independently C₂-C₆ alkylene substituted with hydroxyl or—OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; R₁₃ may be C₁-C₆ alkyl; n may be an integer from 1 to 100;and each X⁻ may be independently an anion.

In some embodiments, a method is provided for controlling microbes on asurface by adding a composition to the surface. The composition mayinclude a cationic polymer of formula (III):

where each R₆ may be independently C₂-C₆ alkylene; each R₇ may beindependently hydrogen, —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or—R₆—N—(R₆—N(R₈)₂)₂; each R₈ may be independently hydrogen or

each R₉ may be independently C₂-C₆ alkylene substituted with hydroxyl or—OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; R₁₃ may be C₁-C₆ alkyl; n may be an integer from 1 to 100;and each X⁻ may be independently an anion.

In some embodiments, a method of inhibiting corrosion on a surface isdisclosed. The method can include contacting the surface with a reactionproduct derived from a reaction of a polyamine or a polyalkyleneimineand a substituted alkyl trialkyl quaternary ammonium salt of formula(I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with a hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl.

The foregoing has outlined rather broadly the features and technicaladvantages of the present disclosure in order that the detaileddescription that follows may be better understood. Additional featuresand advantages of the disclosure will be described hereinafter that formthe subject of the claims of this application. It should be appreciatedby those skilled in the art that the conception and the specificembodiments disclosed may be readily utilized as a basis for modifyingor designing other embodiments for carrying out the same purposes of thepresent disclosure. It should also be realized by those skilled in theart that such equivalent embodiments do not depart from the spirit andscope of the disclosure as set forth in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

A detailed description of the invention is hereafter described withspecific reference being made to the drawings in which:

FIG. 1 shows a graph of surface-tension (mN/m) vs. concentration (wt %)of various quaternary cationic surfactants;

FIG. 2 shows effects of different concentrations of Compound 1 onbacteria reduction in cooling water at various times;

FIG. 3 shows the bacteria concentration as a function of contact timefor various concentrations of Compound 1;

FIG. 4 shows the bacteria concentration as a function of time forCompounds 1-4;

FIG. 5 shows effects of different concentrations of Compound 4 onbacteria concentration in cooling water at various times;

FIG. 6 shows bacteria concentration as a function of contact time forvarious concentrations of Compound 4;

FIG. 7 shows biofilm reduction of a single quat compound compared topolymer quaternary compounds; and

FIG. 8 shows biofilm reduction of a single quat compound compared topolymer quaternary compounds.

DETAILED DESCRIPTION

The present application discloses cationic polymer salts which comprisea reaction product derived from a reaction of a polyamine, analkyleneimine, or a polyalkyleneimine and a substituted alkyl trialkylquaternary ammonium salt. Newly synthesized antimicrobial andanticorrosion cationic polymer salts with multiple quaternary groups aredisclosed herein and may be particularly useful, for example, incontrolling microbial populations or inhibiting corrosion in processwater used in industrial systems. The disclosed compounds showantimicrobial and anticorrosion activity and may be used in anyapplication requiring control of microbes or corrosion inhibition.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentinvention. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety. The materials, methods, and examples disclosed herein areillustrative only, and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional steps or components. The singular forms“a,” “and” and “the” include plural references unless the contextclearly dictates otherwise. The present disclosure also contemplatesother embodiments “comprising,” “consisting of” and “consistingessentially of,” the embodiments or elements presented herein, whetherexplicitly set forth or not.

Unless otherwise indicated, an “alkyl” group as described herein aloneor as part of another group is an optionally substituted linearsaturated monovalent hydrocarbon radical containing from one tothirty-two carbon atoms, or an optionally substituted branched saturatedmonovalent hydrocarbon radical containing three to thirty-two carbonatoms. Examples of unsubstituted alkyl groups include methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl,i-pentyl, s-pentyl, t-pentyl, and the like. Alkyl groups can beunsubstituted or substituted by one or more suitable substituents, asdefined below. Preferably, the substitutions are not within the mainchain or backbone of the polymer salt.

“Arylalkyl” means an aryl group attached to the parent molecule throughan alkylene group. The number of carbon atoms in the aryl group and thealkylene group is selected such that there is a total of about 7 toabout 22 carbon atoms in the arylalkyl group. A preferred arylalkylgroup is benzyl.

The term “-ene” as used as a suffix as part of another group denotes abivalent radical in which a hydrogen atom is removed from each of twoterminal carbons of the group. For example, alkylene denotes a bivalentalkyl group such as methylene (—CH₂—) or ethylene (—CH₂CH₂—). Forclarity, addition of the -ene suffix is not intended to alter thedefinition of the principal word other than denoting a bivalent radical.Thus, continuing the example above, alkylene denotes an optionallysubstituted linear saturated bivalent hydrocarbon radical.

The term “suitable substituent,” as used herein, is intended to mean achemically acceptable functional group that does not negate the activityof the inventive compounds. Such suitable substituents include, but arenot limited to halo groups, perfluoroalkyl groups, perfluoroalkoxygroups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups,oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl orheteroaryl groups, aryloxy or heteroaryloxy groups, arylalkyl orheteroarylalkyl groups, arylalkoxy or heteroarylalkoxy groups, carboxylgroups, heterocyclic groups, cycloalkyl groups, amino groups, alkyl- anddialkylamino groups, carbamoyl groups, alkylcarbonyl groups,alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylamino carbonylgroups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonylgroups, and arylsulfonyl groups. Those skilled in the art willappreciate that many substituents can be substituted by additionalsubstituents.

The cationic polymer salts of the present disclosure exhibit reducedsurface tension in aqueous solution with increasing numbers of alkylchains in the molecule, and are useful as cationic surfactants orfoaming agents (e.g., for use in cleaning formulations or personal careproducts, such as shampoos). The cationic polymer salts have multiplealkyl chains and multiple hydrophilic groups which provide unexpectedphysicochemical properties in comparison with conventional amphiphiliccompounds having one alkyl chain and one hydrophilic group.

In some embodiments, the substituted alkyl trialkyl quaternary ammoniumsalt monomer comprises formula (I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl.

R₁ can comprise C₂-C₃ alkylene substituted with hydroxyl and having anX⁻ end group.

Suitable X⁻ anions can include, but are not limited to, chloride,bromide, fluoride, iodide, acetate, aluminate, cyanate, cyanide,dihydrogen phosphate, dihydrogen phosphite, formate, hydrogen carbonate,hydrogen oxalate, hydrogen sulfate, hydroxide, metaniobate,metavanadate, nitrate, nitrite, thiocyanate, or a combination thereof.In some embodiments, the anion can comprise chloride or bromide.

R₂, R₃, and R₄ can be independently C₁-C₂₂ alkyl. In some embodiments,R₂, R₃, and R₄ can all be methyl. Alternatively, R₂ can be C₆-C₂₂ alkylor C₇-C₂₂ arylalkyl and R₃ and R₄ can be C₁-C₄ alkyl such as methyl, orR₂ and R₃ are C₆-C₂₂ alkyl or C₇-C₂₂ arylalkyl and R₄ is C₁-C₄ alkylsuch as methyl.

Suitable substituted alkyl trialkyl quaternary ammonium salt monomerscan include, but not limited to,3-chloro-2-hydroxypropyl-trimethylammonium chloride;3-chloro-2-hydroxypropyl-dodecyl-dimethylammonium chloride;3-chloro-2-hydroxypropyl-stearyl-dimethylammonium chloride; or acombination thereof.

The polyamine can comprise a polymer of formula (II):

wherein n is an integer from 0 to 100; each R₆ is independently C₂-C₆alkylene; and each R₇ is independently hydrogen or —R₆—NH₂,—R₆—NH—R₆—NH₂, or —R₆—N—(R₆—NH₂)₂.

In the polyamine of formula (II), n can be from 0 to 90, 0 to 80, 0 to70, 0 to 60, 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, 0 to20, 0 to 15, 0 to 10, 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 1 to 90, 1to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 45, 1 to 40, 1 to 35, 1 to 30, 1to 25, 1 to 20, 1 to 15, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to5. In some embodiments, n may be from 2 to 5, 2 to 6, 2 to 7, 2 to 8, 2to 9, 2 to 10, 2 to 25, 2 to 30, 2 to 35, 2 to 40, 2 to 45, 2 to 90, orany sub-range thereof. In other embodiments, n may be from 3 to 100, 3to 90, 3 to 80, 3 to 70, 3 to 60, 3 to 50, 3 to 45, 3 to 40, 3 to 35, 3to 30, 3 to 25, 3 to 10, or any sub-range thereof. In certainembodiments, n is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

In the polyamine of formula (II), R₆ can be C₂-C₃ alkyl. In someembodiments, R₆ can be ethyl.

In the polyamine of formula (II), none of the nitrogens of the polyamineneed be quaternized.

Suitable polyamines can include an alkyleneamine. The alkyleneamine cancomprise, but is not limited to, ethylenediamine, diethylenetriamine,triethylenetetraamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, ora combination thereof.

Suitable polyalkyleneimines can include, but are not limited to,ethyleneimine, propyleneimine, butyleneimine, pentyleneimine,hexyleneimine, heptyleneimine, or a combination thereof.

Suitable polyalkyleneimines can include, but are not limited to,branched, linear, or dendrimer polyethyleneimines.

In some embodiments, the weight average molecular weight of the linear,branched, or dendrimer polyethyleneimine, as measured by gel permeationchromatography, may range from about 200 gm/mol to about 750,000 gm/mol.In some embodiments, the weight average molecular weight of thepolymeric salt may be about 800 gm/mol, about 1,300 gm/mol, about 2,000gm/mol, about 5,000 gm/mol, about 20,000 gm/mol, about 25,000 gm/mol, orabout 750,000 gm/mol.

In some embodiments, the viscosity of the linear, branched, or dendrimerpolyethyleneimine, as measured according to ISO 2555 on a Brookfieldviscometer, may range from about 100 mPa·s to about 30,000 mPa·s. Insome embodiments, the viscosity of the linear, branched, or dendrimerpolyethyleneimine, may range from about 200 mPa·s to about 15,000 mPa·sor from about 200 mPa·s to about 500 mPa·s. In some embodiments, theviscosity of the linear, branched, or dendrimer polyethyleneimine, maybe about 300 mPa·s, about 400 mPa·s, about 500 mPa·s, about 600 mPa·s,or about 1000 mPa·s.

In some embodiments, the ratio of the primary amine/secondaryamine/tertiary amine in the polyethyleneimine may be about 1/0.9/0.6 asmeasured by ¹³CNMR. The amount of amine in the dry polyethyleneimine mayrange from about 10 mmol/gm to about 30 mmol/gm. The amount of amine inthe polyethyleneimine may be about 12 mmol/gm, about 13 mmol/gm, about14 mmol/gm, about 15 mmol/gm, about 16 mmol/gm, about 17 mmol/gm, about18 mmol/gm, about 19 mmol/gm, about 20 mmol/gm, about 21 mmol/gm, orabout 22 mmol/gm.

The molar ratio of the polyamine or polyalkyleneimine to the substitutedalkyl trialkyl quaternary ammonium salt as reactants can range from 1:1to 1:100, 1:1 to 1:90, 1:1 to 1:80, 1:1 to 1:70, 1:1 to 1:60, 1:1 to1:50, 1:1 to 1:45, 1:1 to 1:40, 1:1 to 1:35, 1:1 to 1:30, 1:1 to 1:25,1:1 to 1:20, 1:1 to 1:15, 1:1 to 1:10, 1:1 to 1:9, 1:1 to 1:8, 1:1 to1:7, 1:1 to 1:6, 1:1 to 1:5, 1:1 to 1:4, 1:1 to 1:3, or 1:1 to 1:2.

In some embodiments, a cationic polymer salt is provided which comprisesa reaction product derived from a reaction of a polyamine, analkyleneimine, or a polyalkyleneimine and the substituted alkyl trialkylquaternary ammonium salt of formula (I) as described above, and whereinany one of the following:

(A) the cationic polymer salt has no substitutions within its mainchain, no alkyl-quaternized ammonium within its main chain, andcomprises at least 4 quaternary ammonium groups; or

(B) the cationic polymer salt has one or more terminal tertiary aminegroups having the formula (IV):

wherein R₁₁ is R₁ without the X⁻ end group, and either: the polymer salthas no substitutions within its main chain or at least 1 of R₂, R₃, andR₄ is a C₉-C₂₂ alkyl group; or

(C) R₂ and R₃ of formula (I) are C₆-C₂₂ alkyl or C₇-C₂₂ arylalkyl and R₄is methyl.

In some embodiments, the cationic polymer salt can comprise a polymer offormula (III):

wherein each R₆ is independently C₂-C₆ alkylene; each R₇ isindependently hydrogen, —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or—R₆—N—(R₆—N(R₈)₂)₂; each R₈ is independently hydrogen or

each R₉ is independently C₂-C₆ alkylene substituted with hydroxyl or—OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; R₁₃ is C₁-C₆ alkyl; n is an integer from 1 to 100; and eachX⁻ is independently an anion.

Also provided is a cationic polymer salt having the formula (V):

wherein R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, n, and X⁻ are as defined forformula (III) above, R₁₄ is

and wherein one of the following:

(a) the polymer salt has no substitutions within its main chain, noalkyl-quaternized ammonium within its main chain, and comprises at least4 quaternary ammonium groups; or

(b) either: the polymer salt has no substitutions within its main chainor at least 1 of R₁₀, R₁₁, and R₁₂ of R₁₄ is a C₉-C₂₂ alkyl group; or

(c) the polymer salt includes at least 3 of R₁₂ wherein R₁₂ is C₉-C₁₅alkyl; or

(d) the polymer salt includes at least 3 of R₁₂ wherein R₁₂ is C₁₅-C₂₂alkyl.

In the polymer salt of formula (III) or (V), n can be from 1 to 90, 1 to80, 1 to 70, 1 to 60, 1 to 50, 1 to 45, 1 to 40, 1 to 35, 1 to 30, 1 to25, or any sub-range thereof. In some embodiments, n may be from 2 to25, 2 to 30, 2 to 35, 2 to 40, 2 to 45, 2 to 90, or any sub-rangethereof. In other embodiments, n may be from 3 to 100, 3 to 90, 3 to 80,3 to 70, 3 to 60, 3 to 50, 3 to 45, 3 to 40, 3 to 35, 3 to 30, 3 to 25,or any sub-range thereof. In certain embodiments, n is selected from 1,2, 3, 4, 5, 6, 7, 8, 9, or 10.

In the polymer salt of formula (III) or (V), each R₆ and R₉ can beindependently C₂-C₃ alkylene. In some embodiments, each R₆ can beethylene.

In the polymer salt of formula (III), each R₉ can be hydroxypropylene;R₁₀ and R₁₁ can be methyl; and each R₁₂ can be independently methyl orC₈-C₂₂ alkyl. In some embodiments, at least one R₁₂ is C₈-C₂₂ alkyl.

In other embodiments of the polymer salt of formula (III), R₇ is —R₈,—R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or —R₆—N—(R₆—N(R₈)₂)₂; each R₈ is

each R₉ is independently C₂-C₆ alkylene substituted with hydroxyl or—OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; R₁₃ is C₁-C₆ alkyl; n is an integer from 1 to 100; and eachX⁻ is independently an anion.

In some embodiments of the polymer salt of formula (III), at least oneof R₁₂ may be a saturated C₉-C₁₅ alkyl group. The saturated alkyl groupmay range from C₁₀ to C₁₅, C₁₁ to C₁₅, C₁₂ to C₁₅, C₁₂ to C₁₄, C₁₁ toC₁₄, C₁₀ to C₁₄, C₉ to C₁₄, C₉ to C₁₃, C₁₀ to C₁₃, or C₁₁ to C₁₃. Inother embodiments at least 2, 3, 4, or 5 of R₁₂ may be a saturatedC₉-C₁₅ alkyl group. For instance, at least one of R₁₂ may be a C₁₂ alkylgroup, or, at least 2, 3, 4, or 5 of R₁₂ may be a C₁₂ alkyl group.

In other embodiments of the polymer salt of formula (III), at least oneof R₁₂ may be a saturated C₁₅-C₂₂ alkyl group. The saturated alkyl groupmay range from C₁₆ to C₂₂, C₁₇ to C₂₁, C₁₆ to C₂₀, C₁₈ to C₂₂, C₁₆ toC₁₈, C₁₅ to C₁₈, C₁₅ to C₂₀, or C₁₇ to C₁₉. In other embodiments, atleast 2, 3, 4, or 5 of R₁₂ may be a saturated C₁₅-C₂₂ alkyl group.

In other embodiments, at least one of R₁₂ may be a saturated C₁₂ alkylgroup. In still further embodiments, at least 2, 3, 4, or 5 of R₁₂ maybe a saturated C₁₂ alkyl group.

In other embodiments, at least one of R₁₂ may be a saturated C₁₈ alkylgroup. In still further embodiments, at least 2, 3, 4, or 5 of R₁₂ maybe a saturated C₁₈ alkyl group.

In some embodiments of the polymer salt of formula (III), at least oneR₉ can be R₈, or at least two, three or four R₉ can be R₈. In someembodiments, the cationic salt of formula (III) may comprise at leastthree substituted alkyl trialkyl quaternary ammonium groups. In otherembodiments, there may be at least four, five, or six quaternaryammonium groups. In some embodiments, the quaternary ammonium groups maynot be in the main chain or backbone of the polymer salt, but only onthe branches or side-chains.

In any of the polymer salts as described herein, the polymer salt maynot have any alkyl-quaternary ammoniums within the main chain of thepolymer salt. For example, the polymer salt may not have any—N(CH₃)(CH₃)— nitrogens within the main chain of the polymer salt. Inaddition, the polymer salt may not have any substitutions within themain chain (i.e. backbone) of the polymer salt.

In certain embodiments, the composition of the cationic polymer mayfurther include a carrier. In some embodiments, a surfactant compositionis provided and the surfactant composition may comprise a cationicpolymer salt and a carrier, such as an aqueous carrier.

Suitable carriers can include, but are not limited to, water, analcohol, an aromatic hydrocarbon, an alkylene glycol, an alkyleneglycolalkyl ether, or a combination thereof. For example, suitable carriersinclude methanol, ethanol, propanol, isopropanol, butanol, isobutanol,monoethyleneglycol, ethyleneglycol monobutyl ether, hexylene glycol or acombination thereof.

The preparation of cationic polymer salts can be conducted convenientlyby reacting a polyamine or a polyalkyleneimine or any combinationthereof with a substituted alkyl trialkyl quaternary ammonium salt at apH of at least about 7.5 to form the polymer salt. The molar ratio ofthe polyamine or polyalkyleneimine to the substituted alkyl trialkylquaternary ammonium salt as reactants can range from 1:1 to 1:100, 1:1to 1:90, 1:1 to 1:80, 1:1 to 1:70, 1:1 to 1:60, 1:1 to 1:50, 1:1 to1:45, 1:1 to 1:40, 1:1 to 1:35, 1:1 to 1:30, 1:1 to 1:25, 1:1 to 1:20,1:1 to 1:15, 1:1 to 1:10, 1:1 to 1:9, 1:1 to 1:8, 1:1 to 1:7, 1:1 to1:6, 1:1 to 1:5, 1:1 to 1:4, 1:1 to 1:3, or 1:1 to 1:2. The reactionmixture can be stirred and heated to about 50-100° C. for about 2 to 6hours. A base can be added to maintain a pH of at least about 7.5. Forexample, the reactants can be added to an aqueous solution in a reactorwhile monitoring the pH of the aqueous solution until the completion ofreaction, and adjusting the pH of the aqueous medium to maintain the pHvalue of the aqueous solution equal to or greater than about 7.5.

For example, an alkyleneamine such as diethylenetriamine and asubstituted alkyltrialkyl quaternary ammonium salt such as3-chloro-2-hydroxypropyl trimethylammonium chloride can be added to areaction container equipped with a mechanical stirrer, a thermometer, atemperature controller, a condenser, and an addition funnel. Thereaction mixture is stirred and gently heated to about 60° C. The pHvalue of the reaction is continuously monitored. A base such as sodiumhydroxide (50% aqueous solution) is slowly added to the reactioncontainer and the temperature is held constant at about 60° C. The pHvalue of reaction solution is measured and held constant above about7.5. The reaction temperature is raised to about 85° C. and heldconstant for about 5 hours.

As another example, a polyalkyleneimine such as polyethyleneimine and asubstituted alkyltrialkyl quaternary ammonium salt such as3-chloro-2-hydroxypropyl trimethylammonium chloride can be added to areaction container equipped with a mechanical stirrer, a thermometer, atemperature controller, a condenser, and an addition funnel. Thereaction mixture is stirred and gently heated to about 60° C. The pHvalue of the reaction is continuously monitored. A base such as sodiumhydroxide (50% aqueous solution) is slowly added to the reactioncontainer and the temperature is held constant at about 60° C. The pHvalue of reaction solution is measured and held constant above about7.5. The reaction temperature is raised to about 85° C. and heldconstant for about 5 hours.

The polymer salts described herein are generally random polymers whereinthe exact order of the structural units derived from the polyamine,polyalkyleneimine and substituted alkyl trialkyl quaternary ammoniumsalt is not predetermined.

The polymer salt is generally a reaction product of a mixture that mayalso contain components that are not chemically incorporated into thepolymer. For those reaction products that contain additional componentsin the mixture that are not intended to be incorporated into thepolymer, such additional components typically comprise solvents, pHadjusting agents, buffers, and/or other components known to those ofskill in the art.

The cationic polymer salts as described herein can be used as cationicsurfactants, and can be substituted for conventional quaternary ammoniumcationic surfactants in conventional cleaners and other formulations.

In some embodiments, the weight average molecular weight of the cationicpolymeric salts described herein, as measured by gel permeationchromatography, may range from about 200 gm/mol to about 1,000,000gm/mol. In some embodiments, the weight average molecular weight of thepolymeric salt may be from about 500 gm/mol to about 100,000 gm/mol,from about 500 gm/mol to about 50,000 gm/mol, from about 500 gm/mol toabout 40,000 gm/mol, from about 500 gm/mol to about 30,000 gm/mol, fromabout 5,000 gm/mol to about 30,000 gm/mol, from about 10,000 gm/mol toabout 30,000 gm/mol, from about 500 gm/mol to about 20,000 gm/mol, fromabout 500 gm/mol to about 10,000 gm/mol, or from about 500 gm/mol toabout 5,000 gm/mol.

In some embodiments, a method is provided for controlling microbes on asurface or in process water that includes adding a composition to thesurface or process water. The composition may include a cationic polymerof formula III, as shown above where each R₆ may be independently C₂-C₆alkylene; each R₇ may be independently hydrogen, —R₈, —R₆—N(R₈)₂,—R₆—N(R₈)—R₆—N(R₈)₂, or —R₆—N—(R₆—N(R₈)₂)₂; each R₈ may be independentlyhydrogen or

each R₉ may be independently C₂-C₆ alkylene substituted with hydroxyl or—OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; R₁₃ may be C₁-C₆ alkyl; n may be an integer from 1 to 100;and each X⁻ may be independently an anion.

In other embodiments, a method is provided for controlling microbes on asurface or in process water that includes adding a composition to thesurface or process water. The composition may include a cationic polymerof formula III, as shown above, where each R₆ may be a C₂ alkylene; eachR₇ may be independently —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or—R₆—N—(R₆—N(R₈)₂)₂; each R₈ may be

each R₉ may be independently C₂-C₆ alkylene substituted with hydroxyl or—OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; R₁₃ may be C₁-C₆ alkyl; n may be an integer from 1 to 100;and each X⁻ may be independently an anion.

In certain embodiments, the composition may include a mixture ofdifferent cationic polymer salts. In some embodiments, an antimicrobialcomposition is provided. The antimicrobial composition may comprise acationic polymer salt of formula (III) and an aqueous carrier.

Suitable carriers can include, but are not limited to, water, analcohol, an aromatic hydrocarbon, an alkylene glycol, an alkyleneglycolalkyl ether, or a combination thereof. For example, suitable carriersinclude methanol, ethanol, propanol, isopropanol, butanol, isobutanol,monoethyleneglycol, ethyleneglycol monobutyl ether, or a combinationthereof.

In some embodiments, the composition added to the surface or processwater may include a cationic polymer salt, such as Compound 1, Compound2, Compound 3, or Compound 4.

In some embodiments, the composition added to the surface or processwater may include Compound 1. Compound 1 includes five quaternary aminegroups, wherein four of the five comprise a saturated C₁₂ alkyl group.

In certain embodiments, the composition includes a biocide, a carrier,and cationic polymer salt selected from Compound 1, Compound 2, Compound3, Compound 4, Compound 5, Compound 6, Compound 7, Compound 8, Compound9, Compound 10, Compound 11, Compound 12, Compound 13, or anycombination thereof. In certain embodiments, the composition includes abiocide, a carrier, and cationic polymer salt selected from Compound 14,Compound 15, or Compound 16. In some embodiments, the composition mayconsist of a cationic polymer salt of formula III. In some embodiments,the composition may consist of a cationic polymer salt of formula IIIand water. In some embodiments, the composition may consist of acationic polymer salt of formula III, water, and a biocide.

Biocides suitable for use may be oxidizing or non-oxidizing biocides.Oxidizing biocides include, but are not limited to, bleach, chlorine,bromine, chlorine dioxide and materials capable of releasing chlorineand bromine. Non-oxidizing biocides include, but are not limited to,glutaraldehyde, isothiazolin, 2,2-dibromo-3-nitrilopropionamide,2-bromo-2-nitropropane-1,3 diol,1-bromo-1-(bromomethyl)-1,3-propanedicarbonitrile,tetrachloroisophthalonitrile, alkyldimethylbenzylammonium chloride,dimethyl dialkyl ammonium chloride, didecyl dimethyl ammonium chloride,poly(oxyethylene(dimethyliminio)ethylene(dimethyliminio)ethylenedichloride, methylene bisthiocyanate, 2-decylthioethanamine,tetrakishydroxymethyl phosphonium sulfate, dithiocarbamate,cyanodithioimidocarbonate, 2-methyl-5-nitroimidazole-1-ethanol,2-(2-bromo-2-nitroethenyl)furan, beta-bromo-beta-nitrostyrene,beta-nitrostyrene, beta-nitrovinyl furan, 2-bromo-2-bromomethylglutaronitrile, bis(trichloromethyl) sulfone,S-(2-hydroxypropyl)thiomethanesulfonate,tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione,2-(thiocyanomethylthio)benzothiazole, 2-bromo-4′-hydroxyacetophenone,1,4-bis(bromoacetoxy)-2-butene, bis(tributyltin)oxide,2-(tert-butylamino)-4-chloro-6-(ethylamino)-s-triazine, dodecylguanidineacetate, dodecylguanidine hydrochloride, coco alkyldimethylamine oxide,n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride,7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid,4,5-dichloro-2-n-octyl-4-isothiazoline-3-one,5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one.

In other embodiments, corrosion inhibitors may be added when needed toreduce corrosion of the metal in the industrial water system. Corrosioninhibitors for multi-metal protection are typically triazoles, such as,but not limited to, benzotriazole, halogenated triazoles, andnitro-substituted azoles.

In some embodiments, dispersants may be added to keep particulate matterpresent in the water of an industrial water system dispersed, so that itdoes not agglomerate and cause fouling during the cleaning anddisinfecting process. Polymeric dispersants may be acrylic acid,polymaleic acid, copolymers of acrylic acid with sulfonated monomers andalkyl esters thereof. These polymers may include terpolymers of acrylicacid, acrylamide and sulfonated monomers. These polymers may alsoinclude quad-polymers consisting of acrylic acid and three othermonomers.

In other embodiments, a method is provided for controlling microbes inprocess water or on a surface by adding to the process water or surfacea composition that includes a cationic polymer salt of formula III. Inother embodiments, the method may include adding a composition to thesurface or process water that includes a cationic polymer salt offormula III, where n may be greater than 1 and each R₇ may beindependently hydrogen, —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or—R₆—N—(R₆—N(R₈)₂)₂. The cationic polymer salt may be added to thesurface or process water as an aqueous composition or as a dry powder.The cationic polymer salt may be added continuously or it may be addedintermittently when more antimicrobial activity may be needed.

In other embodiments, the cationic polymer salt in the composition maybe Compound 1, Compound 2, Compound 3, Compound 4, Compound 5, Compound6, Compound 7, Compound 8, Compound 9, Compound 10, Compound 11,Compound 12, Compound 13, Compound 14, Compound 15, or any combinationthereof. Chemical structures for Compounds 5-13 are shown below in theExamples.

In some embodiments, the cationic polymer salt may be added to theprocess water in an amount ranging from about 1 ppm to about 1000 ppm.In other embodiments, the amount of added cationic polymer salt in theprocess water may range from about 5 ppm to about 100 ppm, about 5 ppmto about 50 ppm, about 5 ppm to about 40 ppm, about 5 ppm to about 30ppm, about 10 ppm to about 60 ppm, about 10 ppm to about 50 ppm, about10 ppm to about 40 ppm, about 10 ppm to about 30 ppm, about 20 ppm toabout 60 ppm, about 20 ppm to about 50 ppm, about 20 ppm to about 40ppm, or about 20 ppm to about 30 ppm. In some embodiments, the cationicpolymer salt may be added to the process water to an amount ranging fromabout 100 ppm to about 1000, about 125 to about 1000, about 250 to about1000, or about 500 to about 1000.

In some embodiments, the method may be used to clean and disinfectsurfaces or process water in any industrial water system. Theseindustrial water system may include, but is not limited to cooling watersystems, including open recirculating systems, closed and once-throughcooling water systems, boilers and boiler water systems, petroleum wellsystems, downhole formations, geothermal wells and other oil fieldapplications, mineral washing systems, flotation and benefactionsystems, paper mill digesters, washers, bleach plants, stock chests,white water systems, paper machine surfaces, black liquor evaporators inthe pulp industry, gas scrubbers and air washers, continuous castingprocesses in the metallurgical industry, air conditioning andrefrigeration systems, industrial and petroleum process water, indirectcontact cooling and heating water, water reclamation systems, waterpurification systems, membrane filtration water systems, food processingstreams (meat, vegetable, sugar beets, sugar cane, grain, poultry, fruitand soybean), waste treatment systems, clarifiers, liquid-solidapplications, municipal sewage treatment, municipal water systems,potable water systems, aquifers, water tanks, sprinkler systems, andwater heaters.

In some embodiments, the industrial water system may cooling watersystems, including open recirculating, closed and once-through coolingwater systems, paper machine surfaces, food processing streams, wastetreatment systems and potable water systems.

In still further embodiments, the method of treating process water mayinclude the step of contacting a spore or a thermophile in the processwater with the composition. The composition may partially inactivate orkill the spore or thermophile. In other embodiments, the method mayinclude the step of contacting a bacterium in the process water with thecomposition. The composition may kill the bacterium or partially killbacteria or microbes in the process water.

In another embodiment, the composition used in the method may include abiocide. The biocide may be any of those listed above or other knownagent. The amount of biocide in the composition may be an effectiveamount that provides adequate control of the microbes in the process.

Another aspect of the invention is a composition for inhibitingcorrosion at a surface. The composition comprises the cationic polymersalt as described herein and a component comprising an organic solvent,a corrosion inhibitor, an organic sulfur compound, an asphalteneinhibitor, a paraffin inhibitor, a scale inhibitor, an emulsifier, awater clarifier, a dispersant, an emulsion breaker, a gas hydrateinhibitor, a biocide, a pH modifier, a surfactant, or a combinationthereof.

The composition can comprise, for example, from about 0.1 to about 20wt. % of one or more cationic polymer salts and from about 80 to about99.9 wt. % of the component; from about 0.1 to about 20 wt. % of one ormore cationic polymer salts, from about 1 to about 60 wt. % of thecomponent and from about 20 to about 98.9 wt. % water; from about 10 toabout 20 wt. % of one or more cationic polymer salts, from about 30 toabout 40 wt. % of the component and from about 40 to about 60 wt. %water; or from about 15 to about 20 wt. % of one or more cationicpolymer salts, from about 1 to about 10 wt. % of the component and fromabout 70 to about 84 wt. % water.

The component of the composition can comprise an organic solvent. Thecomposition can comprise from about 1 to 80 wt. %, from about 5 to 50wt. %, or from about 10 to 35 wt. % of the one or more organic solvents,based on total weight of the composition. The organic solvent cancomprise an alcohol, a hydrocarbon, a ketone, an ether, an alkyleneglycol, a glycol ether, an amide, a nitrile, a sulfoxide, an ester, or acombination thereof. Examples of suitable organic solvents include, butare not limited to, methanol, ethanol, propanol, isopropanol, butanol,2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, methyleneglycol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether,ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, pentane,hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane,diesel, toluene, xylene, heavy aromatic naphtha, cyclohexanone,diisobutylketone, diethyl ether, propylene carbonate,N-methylpyrrolidinone, N,N-dimethylformamide, or a combination thereof.

In addition to the component, the composition can comprise water.

The component of the composition can comprise a corrosion inhibitor inaddition to the one or more cationic polymer salts. The composition cancomprise from about 0.1 to 20 wt. %, 0.1 to 10 wt. %, or 0.1 to 5 wt. %of the one or more additional corrosion inhibitors, based on totalweight of the composition. A composition of the invention can comprisefrom 0 to 10 percent by weight of the one or more additional corrosioninhibitors, based on total weight of the composition. The compositioncan comprise 1.0 wt. %, 1.5 wt. %, 2.0 wt. %, 2.5 wt. %, 3.0 wt. %, 3.5wt. %, 4.0 wt. %, 4.5 wt. %, 5.0 wt. %, 5.5 wt. %, 6.0 wt. %, 6.5 wt. %,7.0 wt. %, 7.5 wt. %, 8.0 wt. %, 8.5 wt. %, 9.0 wt. %, 9.5 wt. %, 10.0wt. %, 10.5 wt. %, 11.0 wt. %, 11.5 wt. %, 12.0 wt. %, 12.5 wt. %, 13.0wt. %, 13.5 wt. %, 14.0 wt. %, 14.5 wt. %, or 15.0 wt. % by weight ofthe one or more additional corrosion inhibitors, based on total weightof the composition. Each system can have its own requirements, and theweight percent of one or more additional corrosion inhibitors in thecomposition can vary with the system in which it is used.

The one or more additional corrosion inhibitors can comprise animidazoline compound, a quaternary ammonium compound, a pyridiniumcompound, or a combination thereof.

The one or more additional corrosion inhibitor component can comprise animidazoline. The imidazoline can be, for example, imidazoline derivedfrom a diamine, such as ethylene diamine (EDA), diethylene triamine(DETA), triethylene tetraamine (TETA) etc. and a long chain fatty acidsuch as tall oil fatty acid (TOFA). The imidazoline can be animidazoline of Formula (1A) or an imidazoline derivative. Representativeimidazoline derivatives include an imidazolinium compound of Formula(2A) or a bis-quaternized compound of Formula (3A).

The one or more additional corrosion inhibitor component can include animidazoline of Formula (1A):

wherein R^(10a) is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R^(11a)is hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, or C₁-C₆ arylalkyl; andR^(12a) and R^(13a) are independently hydrogen or a C₁-C₆ alkyl group.Preferably, the imidazoline includes an R^(10a) which is the alkylmixture typical in tall oil fatty acid (TOFA), and R^(11a), R^(12a) andR^(13a) are each hydrogen.

The one or more additional corrosion inhibitor component can include animidazolinium compound of Formula (2A):

wherein R^(10a) is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R^(11a)and R^(14a) are independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl,or C₁-C₆ arylalkyl; R^(12a) and R^(14a) are independently hydrogen or aC₁-C₆ alkyl group; and X⁻ is a halide (such as chloride, bromide, oriodide), carbonate, sulfonate, phosphate, or the anion of an organiccarboxylic acid (such as acetate). Preferably, the imidazoliniumcompound includes 1-benzyl-1-(2-hydroxyethyl)-2-tall-oil-2-imidazoliniumchloride.

The one or more additional corrosion inhibitors can comprise abis-quaternized compound having the formula (3A):

wherein:

R^(1a) and R^(2a) are each independently unsubstituted branched, chainor ring alkyl or alkenyl having from 1 to about 29 carbon atoms;partially or fully oxygenized, sulfurized, and/or phosphorylizedbranched, chain, or ring alkyl or alkenyl having from 1 to about 29carbon atoms; or a combination thereof;

R^(3a) and R^(4a) are each independently unsubstituted branched, chainor ring alkylene or alkenylene having from 1 to about 29 carbon atoms;partially or fully oxygenized, sulfurized, and/or phosphorylizedbranched, chain, or ring alkylene or alkenylene having from 1 to about29 carbon atoms; or a combination thereof;

L₁ and L₂ are each independently absent, H, —COOH, —SO₃H, —PO₃H₂,—COOR^(5a), —CONH₂, —CONHR^(5a), or —CON(R^(5a))₂;

R^(5a) is each independently a branched or unbranched alkyl, aryl,alkylaryl, alkylheteroaryl, cycloalkyl, or heteroaryl group having from1 to about 10 carbon atoms;

n is 0 or 1, and when n is 0, L₂ is absent or H;

x is from 1 to about 10; and

y is from 1 to about 5. Preferably, R^(1a) and R^(2a) are eachindependently C₆-C₂₂ alkyl, C₈-C₂₀ alkyl, C₁₂-C₁₈ alkyl, C₁₆-C₁₈ alkyl,or a combination thereof; R^(3a) and R^(4a) are C₁-C₁₀ alkylene, C₂-C₈alkylene, C₂-C₆ alkylene, or C₂-C₃ alkylene; n is 0 or 1; x is 2; y is1; R₃ and R₄ are —C₂H₂—; L₁ is —COOH, —SO₃H, or —PO₃H₂; and L₂ isabsent, H, —COOH, —SO₃H, or —PO₃H₂. For example, R^(1a) and R^(2a) canbe derived from a mixture of tall oil fatty acids and are predominantlya mixture of C₁₇H₃₃ and C₁₇H₃₁ or can be C₁₆-C₁₈ alkyl; R^(3a) andR^(4a) can be C₂-C₃ alkylene such as —C₂H₂—; n is 1 and L₂ is —COOH or nis 0 and L₂ is absent or H; x is 2; y is 1; R^(1a) and R^(4a) are—C₂H₂—; and L₁ is —COOH.

It should be appreciated that the number of carbon atoms specified foreach group of formula (3A) refers to the main chain of carbon atoms anddoes not include carbon atoms that may be contributed by substituents.

The one or more additional corrosion inhibitors can comprise abis-quaternized imidazoline compound having the formula (3A) whereinR^(1a) and R^(2a) are each independently C₆-C₂₂ alkyl, C₈-C₂₀ alkyl,C₁₂-C₁₈ alkyl, or C₁₆-C₁₈ alkyl or a combination thereof; R^(4a) isC₁-C₁₀ alkylene, C₂-C₈ alkylene, C₂-C₆ alkylene, or C₂-C₃ alkylene; x is2; y is 1; n is 0; L₁ is —COOH, —SO₃H, or —PO₃H₂; and L₂ is absent or H.Preferably, a bis-quaternized compound has the formula (3A) whereinR^(1a) and R^(2a) are each independently C₁₆-C₁₈ alkyl; R^(4a) is—C₂H₂—; x is 2; y is 1; n is 0; L₁ is —COOH, —SO₃H, or —PO₃H₂ and L₂ isabsent or H.

The one or more additional corrosion inhibitors can be a quaternaryammonium compound of Formula (4A):

wherein R^(1a), R^(2a), and R^(3a) are independently C₁ to C₂₀ alkyl,R^(4a) is methyl or benzyl, and X⁻ is a halide or methosulfate.

Suitable alkyl, hydroxyalkyl, alkylaryl, arylalkyl or aryl aminequaternary salts include those alkylaryl, arylalkyl and aryl aminequaternary salts of the formula [N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻] whereinR^(5a), R^(6a), R^(7a), and R^(8a) contain one to 18 carbon atoms, and Xis Cl, Br or I. For the quaternary salts, R_(5a), R^(6a), R^(7a), andR^(8a) can each be independently alkyl (e.g., C₁-C₁₈ alkyl),hydroxyalkyl (e.g., C₁-C₁₈ hydroxyalkyl), and arylalkyl (e.g., benzyl).The mono or polycyclic aromatic amine salt with an alkyl or alkylarylhalide include salts of the formula [N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻]wherein R^(5a), R^(6a), R^(7a), and R^(8a) contain one to 18 carbonatoms and at least one aryl group, and X is Cl, Br or I.

Suitable quaternary ammonium salts include, but are not limited to, atetramethyl ammonium salt, a tetraethyl ammonium salt, a tetrapropylammonium salt, a tetrabutyl ammonium salt, a tetrahexyl ammonium salt, atetraoctyl ammonium salt, a benzyltrimethyl ammonium salt, abenzyltriethyl ammonium salt, a phenyltrimethyl ammonium salt, aphenyltriethyl ammonium salt, a cetyl benzyldimethyl ammonium salt, ahexadecyl trimethyl ammonium salt, a dimethyl alkyl benzyl quaternaryammonium salt, a monomethyl dialkyl benzyl quaternary ammonium salt, ora trialkyl benzyl quaternary ammonium salt, wherein the alkyl group hasabout 6 to about 24 carbon atoms, about 10 and about 18 carbon atoms, orabout 12 to about 16 carbon atoms. The quaternary ammonium salt can be abenzyl trialkyl quaternary ammonium salt, a benzyl triethanolaminequaternary ammonium salt, or a benzyl dimethylaminoethanolaminequaternary ammonium salt.

The one or more additional corrosion inhibitor component can comprise apyridinium salt such as those represented by Formula (5A):

wherein R^(9a) is an alkyl group, an aryl group, or an arylalkyl group,wherein said alkyl groups have from 1 to about 18 carbon atoms and X⁻ isa halide such as chloride, bromide, or iodide. Among these compounds arealkyl pyridinium salts and alkyl pyridinium benzyl quats. Exemplarycompounds include methyl pyridinium chloride, ethyl pyridinium chloride,propyl pyridinium chloride, butyl pyridinium chloride, octyl pyridiniumchloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetylpyridinium chloride, benzyl pyridinium chloride and an alkyl benzylpyridinium chloride, preferably wherein the alkyl is a C₁-C₆ hydrocarbylgroup. Preferably, the pyridinium compound includes benzyl pyridiniumchloride.

The one or more additional corrosion inhibitor components can includeadditional corrosion inhibitors such as phosphate esters, monomeric oroligomeric fatty acids, or alkoxylated amines.

The one or more additional corrosion inhibitor component can comprise aphosphate ester. Suitable mono-, di- and tri-alkyl as well as alkylarylphosphate esters and phosphate esters of mono, di, and triethanolaminetypically contain between from 1 to about 18 carbon atoms. Preferredmono-, di- and trialkyl phosphate esters, alkylaryl or arylalkylphosphate esters are those prepared by reacting a C₃-C₁₈ aliphaticalcohol with phosphorous pentoxide. The phosphate intermediateinterchanges its ester groups with triethylphosphate producing a morebroad distribution of alkyl phosphate esters.

Alternatively, the phosphate ester can be made by admixing with an alkyldiester, a mixture of low molecular weight alkyl alcohols or diols. Thelow molecular weight alkyl alcohols or diols preferably include C₆ toC₁₀ alcohols or diols. Further, phosphate esters of polyols and theirsalts containing one or more 2-hydroxyethyl groups, and hydroxylaminephosphate esters obtained by reacting polyphosphoric acid or phosphoruspentoxide with hydroxylamines such as diethanolamine or triethanolamineare preferred.

The one or more additional corrosion inhibitor component can include amonomeric or oligomeric fatty acid. Preferred monomeric or oligomericfatty acids are C₁₄-C₂₂ saturated and unsaturated fatty acids as well asdimer, trimer and oligomer products obtained by polymerizing one or moreof such fatty acids.

The one or more additional corrosion inhibitor component can comprise analkoxylated amine. The alkoxylated amine can be an ethoxylated alkylamine. The alkoxylated amine can be ethoxylated tallow amine.

The component of the composition can comprise an organic sulfurcompound, such as a mercaptoalkyl alcohol, mercaptoacetic acid,thioglycolic acid, 3,3′-dithiodipropionic acid, sodium thiosulfate,thiourea, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammoniumthiosulfate, sodium thiocyanate, ammonium thiocyanate, sodiummetabisulfite, or a combination thereof. Preferably, the mercaptoalkylalcohol comprises 2-mercaptoethanol. Such compounds are used assynergists in the composition. The organic sulfur compound canconstitute 0.5 to 15 wt. % of the composition, based on total weight ofthe composition, preferably about 1 to about 10 wt. % and morepreferably about 1 to about 5 wt. %. The organic sulfur compound canconstitute 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 wt. % ofthe composition.

The component of the composition can further include a demulsifier.Preferably, the demulsifier comprises an oxyalkylate polymer, such as apolyalkylene glycol. The demulsifier can constitute from about 0.1 to 10wt. %, from about 0.5 to 5 wt. %, or from about 0.5 to 4 wt. of thecomposition, based on total weight of the composition. The demulsifiercan constitute 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 wt. % of thecomposition.

The component of the composition can include an asphaltene inhibitor.The composition can comprise from about 0.1 to 10 wt. %, from about 0.1to 5 wt. %, or from about 0.5 to 4 wt. % of an asphaltene inhibitor,based on total weight of the composition. Suitable asphaltene inhibitorsinclude, but are not limited to, aliphatic sulfonic acids; alkyl arylsulfonic acids; aryl sulfonates; lignosulfonates; alkylphenol/aldehyderesins and similar sulfonated resins; polyolefin esters; polyolefinimides; polyolefin esters with alkyl, alkylenephenyl or alkylenepyridylfunctional groups; polyolefin amides; polyolefin amides with alkyl,alkylenephenyl or alkylenepyridyl functional groups; polyolefin imideswith alkyl, alkylenephenyl or alkylenepyridyl functional groups;alkenyl/vinyl pyrrolidone copolymers; graft polymers of polyolefins withmaleic anhydride or vinyl imidazole; hyperbranched polyester amides;polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkylsuccinates, sorbitan monooleate, and polyisobutylene succinic anhydride.

The component of the composition can include a paraffin inhibitor. Thecomposition can comprise from about 0.1 to 10 wt. %, from about 0.1 to 5wt. %, or from about 0.5 to 4 wt. % of a paraffin inhibitor, based ontotal weight of the composition. Suitable paraffin inhibitors include,but are not limited to, paraffin crystal modifiers, anddispersant/crystal modifier combinations. Suitable paraffin crystalmodifiers include, but are not limited to, alkyl acrylate copolymers,alkyl acrylate vinylpyridine copolymers, ethylene vinyl acetatecopolymers, maleic anhydride ester copolymers, branched polyethylenes,naphthalene, anthracene, microcrystalline wax and/or asphaltenes.Suitable paraffin dispersants include, but are not limited to, dodecylbenzene sulfonate, oxyalkylated alkylphenols, and oxyalkylatedalkylphenolic resins.

The component of the composition can include a scale inhibitor. Thecomposition can comprise from about 0.1 to 20 wt. %, from about 0.5 to10 wt. %, or from about 1 to 10 wt. % of a scale inhibitor, based ontotal weight of the composition. Suitable scale inhibitors include, butare not limited to, phosphates, phosphate esters, phosphoric acids,phosphonates, phosphonic acids, polyacrylamides, salts ofacrylamidomethyl propane sulfonate/acrylic acid copolymer (AMPS/AA),phosphinated maleic copolymer (PHOS/MA), and salts of a polymaleicacid/acrylic acid/acrylamidomethyl propane sulfonate terpolymer(PMA/AA/AMPS).

The component of the composition can include an emulsifier. Thecomposition can comprise from about 0.1 to 10 wt. %, from about 0.5 to 5wt. %, or from about 0.5 to 4 wt. % of an emulsifier, based on totalweight of the composition. Suitable emulsifiers include, but are notlimited to, salts of carboxylic acids, products of acylation reactionsbetween carboxylic acids or carboxylic anhydrides and amines, and alkyl,acyl and amide derivatives of saccharides (alkyl-saccharideemulsifiers).

The component of the composition can include a water clarifier. Thecomposition can comprise from about 0.1 to 10 wt. %, from about 0.5 to 5wt. %, or from about 0.5 to 4 wt. % of a water clarifier, based on totalweight of the composition. Suitable water clarifiers include, but arenot limited to, inorganic metal salts such as alum, aluminum chloride,and aluminum chlorohydrate, or organic polymers such as acrylic acidbased polymers, acrylamide based polymers, polymerized amines,alkanolamines, thiocarbamates, and cationic polymers such asdiallyldimethylammonium chloride (DADMAC).

The component of the composition can include a dispersant. Thecomposition can comprise from about 0.1 to 10 wt. %, from about 0.5 to 5wt. %, or from about 0.5 to 4 wt. % of a dispersant, based on totalweight of the composition. Suitable dispersants include, but are notlimited to, aliphatic phosphonic acids with 2-50 carbons, such ashydroxyethyl diphosphonic acid, and aminoalkyl phosphonic acids, e.g.polyaminomethylene phosphonates with 2-10 N atoms e.g. each bearing atleast one methylene phosphonic acid group; examples of the latter areethylenediamine tetra(methylene phosphonate), diethylenetriaminepenta(methylene phosphonate), and the triamine- andtetramine-polymethylene phosphonates with 2-4 methylene groups betweeneach N atom, at least 2 of the numbers of methylene groups in eachphosphonate being different. Other suitable dispersion agents includelignin, or derivatives of lignin such as lignosulfonate and naphthalenesulfonic acid and derivatives.

The component of the composition can include an emulsion breaker. Thecomposition can comprise from about 0.1 to 10 wt. %, from about 0.5 to 5wt. %, or from about 0.5 to 4 wt. % of an emulsion breaker, based ontotal weight of the composition. Suitable emulsion breakers include, butare not limited to, dodecylbenzylsulfonic acid (DDBSA), the sodium saltof xylenesulfonic acid (NAXSA), epoxylated and propoxylated compounds,anionic, cationic and nonionic surfactants, and resins, such as phenolicand epoxide resins.

The component of the composition can include a hydrogen sulfidescavenger. The composition can comprise from about 1 to 50 wt. %, fromabout 1 to 40 wt. %, or from about 1 to 30 wt. % of a hydrogen sulfidescavenger, based on total weight of the composition. Suitable additionalhydrogen sulfide scavengers include, but are not limited to, oxidants(e.g., inorganic peroxides such as sodium peroxide or chlorine dioxide);aldehydes (e.g., of 1-10 carbons such as formaldehyde, glyoxal,glutaraldehyde, acrolein, or methacrolein; triazines (e.g.,monoethanolamine triazine, monomethylamine triazine, and triazines frommultiple amines or mixtures thereof); condensation products of secondaryor tertiary amines and aldehydes, and condensation products of alkylalcohols and aldehydes.

The component of the composition can include a gas hydrate inhibitor.The composition can comprise from about 0.1 to 25 wt. %, from about 0.5to 20 wt. %, or from about 1 to 10 wt. % of a gas hydrate inhibitor,based on total weight of the composition. Suitable gas hydrateinhibitors include, but are not limited to, thermodynamic hydrateinhibitors (THI), kinetic hydrate inhibitors (KHI), andanti-agglomerates (AA). Suitable thermodynamic hydrate inhibitorsinclude, but are not limited to, sodium chloride, potassium chloride,calcium chloride, magnesium chloride, sodium bromide, formate brines(e.g. potassium formate), polyols (such as glucose, sucrose, fructose,maltose, lactose, gluconate, monoethylene glycol, diethylene glycol,triethylene glycol, mono-propylene glycol, dipropylene glycol,tripropylene glycols, tetrapropylene glycol, monobutylene glycol,dibutylene glycol, tributylene glycol, glycerol, diglycerol,triglycerol, and sugar alcohols (e.g. sorbitol, mannitol)), methanol,propanol, ethanol, glycol ethers (such as diethyleneglycolmonomethylether, ethyleneglycol monobutylether), and alkyl or cyclicesters of alcohols (such as ethyl lactate, butyl lactate, methylethylbenzoate).

The component of the composition can include a kinetic hydrateinhibitor. The composition can comprise from about 0.1 to 25 wt. %, fromabout 0.5 to 20 wt. %, or from about 1 to 10 wt. % of a kinetic hydrateinhibitor, based on total weight of the composition. Suitable kinetichydrate inhibitors and anti-agglomerates include, but are not limitedto, polymers and copolymers, polysaccharides (such ashydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), starch,starch derivatives, and xanthan), lactams (such as polyvinylcaprolactam,polyvinyl lactam), pyrrolidones (such as polyvinyl pyrrolidone ofvarious molecular weights), surfactants (such as fatty acid salts,ethoxylated alcohols, propoxylated alcohols, sorbitan esters,ethoxylated sorbitan esters, polyglycerol esters of fatty acids, alkylglucosides, alkyl polyglucosides, alkyl sulfates, alkyl sulfonates,alkyl ester sulfonates, alkyl aromatic sulfonates, alkyl betaine, alkylamido betaines), hydrocarbon based dispersants (such as lignosulfonates,iminodisuccinates, polyaspartates), amino acids, and proteins.

The component of the composition can include a biocide. The compositioncan comprise from about 0.1 to 10 wt. %, from about 0.5 to 5 wt. %, orfrom about 0.5 to 4 wt. % of a biocide, based on total weight of thecomposition. Suitable biocides include, but are not limited to,oxidizing and non-oxidizing biocides. Suitable non-oxidizing biocidesinclude, for example, aldehydes (e.g., formaldehyde, glutaraldehyde, andacrolein), amine-type compounds (e.g., quaternary amine compounds andcocodiamine), halogenated compounds (e.g., 2-bromo-2-nitropropane-3-diol(Bronopol) and 2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfurcompounds (e.g., isothiazolone, carbamates, and metronidazole), andquaternary phosphonium salts (e.g., tetrakis(hydroxymethyl)-phosphoniumsulfate (THPS)). Suitable oxidizing biocides include, for example,sodium hypochlorite, trichloroisocyanuric acids, dichloroisocyanuricacid, calcium hypochlorite, lithium hypochlorite, chlorinatedhydantoins, stabilized sodium hypobromite, activated sodium bromide,brominated hydantoins, chlorine dioxide, ozone, and peroxides.

The component of the composition can include a pH modifier. Thecomposition can comprise from about 0.1 to 20 wt. %, from about 0.5 to10 wt. %, or from about 0.5 to 5 wt. % of a pH modifier, based on totalweight of the composition. Suitable pH modifiers include, but are notlimited to, alkali hydroxides, alkali carbonates, alkali bicarbonates,alkaline earth metal hydroxides, alkaline earth metal carbonates,alkaline earth metal bicarbonates and mixtures or combinations thereof.Exemplary pH modifiers include sodium hydroxide, potassium hydroxide,calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate,sodium bicarbonate, potassium bicarbonate, magnesium oxide, andmagnesium hydroxide.

The component of the composition can include a surfactant. Thecomposition can comprise from about 0.1 to 10 wt. %, from about 0.5 to 5wt. %, or from about 0.5 to 4 wt. % of a surfactant, based on totalweight of the composition. Suitable surfactants include, but are notlimited to, anionic surfactants and nonionic surfactants. Anionicsurfactants include alkyl aryl sulfonates, olefin sulfonates, paraffinsulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylatesand alkyl ether carboxylates, and alkyl and ethoxylated alkyl phosphateesters, and mono and dialkyl sulfosuccinates and sulfosuccinamates.Nonionic surfactants include alcohol alkoxylates, alkylphenolalkoxylates, block copolymers of ethylene, propylene and butyleneoxides, alkyl dimethyl amine oxides, alkyl-bis(2-hydroxyethyl)amineoxides, alkyl amidopropyl dimethyl amine oxides,alkylamidopropyl-bis(2-hydroxyethyl)amine oxides, alkyl polyglucosides,polyalkoxylated glycerides, sorbitan esters and polyalkoxylated sorbitanesters, and alkoyl polyethylene glycol esters and diesters. Alsoincluded are betaines and sultanes, amphoteric surfactants such as alkylamphoacetates and amphodiacetates, alkyl amphopropionates andamphodipropionates, and alkyliminodipropionate.

Corrosion inhibitor compositions made according to the invention canfurther include additional functional agents or additives that provide abeneficial property. For example, additional agents or additives can besequestrants, solubilizers, lubricants, buffers, cleaning agents, rinseaids, preservatives, binders, thickeners or other viscosity modifiers,processing aids, carriers, water-conditioning agents, foam inhibitors orfoam generators, threshold agents or systems, aesthetic enhancing agents(i.e., dyes, odorants, perfumes), or other additives suitable forformulation with a corrosion inhibitor composition, and mixturesthereof. Additional agents or additives will vary according to theparticular corrosion inhibitor composition being manufactured and itsintend use as one skilled in the art will appreciate.

Alternatively, the compositions can not contain any of the additionalagents or additives.

Additionally, the corrosion inhibitors of the invention can beformulated into compositions comprising the following components. Theseformulations include the ranges of the components listed and canoptionally include additional agents. The values in the Tables below areweight percents.

Component 1 2 3 4 5 6 7 8 9 10 11 12 Cationic 0.1-20 0.1-20 0.1-20  0.1-20 0.1-20  0.1-20   10-20  10-20 10-20  10-20  10-20 0.1-20 polymersalt Organic solvent  5-40 — 5-50 — 5-50 5-50   5-40 — 5-50 — —  10-20Additional 0.1-20 0.1-20 — — — —  0.1-20  0.1-20 — — — 0.1-20 corrosioninhibitor Asphaltene 0.1-5  0.1-5  0.1-5   0.1-5 — — 0.1-5 0.1-5 0.1-5  — — 0.1-5  inhibitor Scale inhibitor  1-10  1-10 1-10   1-10 1-10 —  1-10   1-10 1-10 1-10 —  1-10 Gas hydrate — — — — — — — — — — — 0.1-25inhibitor Biocide 0.5-5  0.5-5  0.5-5   0.5-5 0.5-5   0.5-5   0.5-50.5-5 0.5-5   0.5-5   0.5-5  Water 0.00  0-40 0-10   0-60 0-15 0-25 0.00  0-40 0-10 0-65  0-75

Component 13 14 15 16 17 18 19 20 21 22 23 24 Cationic 0.1-20 0.1-200.1-20 0.1-20 0.1-20 0.1-20  10-20  10-20  10-20 10-20  10-20 10-20 polymer salt Organic solvent —  10-20 —  10-35  10-35 —  10-15 — — 10-35 10-35 — Additional 0.1-20 0.1-20 0.1-20 0.1-20 0.1-20 0.1-20 0.1-200.1-20 0.1-20 0.1-20  0.1-20 0.1-20  corrosion inhibitor Asphaltene0.1-5  — — — — — 0.1-5  — — — — — inhibitor Scale inhibitor  1-10  1-10— —  1-10 —  1-10  1-10 — — — 1-10 Gas hydrate 0.1-25 0.1-25 0.1-25 — —— 0.1-25 0.1-25 0.1-25 — 0.1-25 — inhibitor Biocide — — — — — 0.5-5 0.5-5  0.5-5  0.5-5  0.5-5  — — Water  0-20  0-5  0-35  0-25  0-15  0-550.00  0-20  0-30  0-20 0.00 0-50

Another aspect of the invention is a method of inhibiting corrosion at asurface. The method comprises either: contacting the surface with acationic polymer salt to inhibit corrosion on the surface; contactingthe surface with a composition comprising the cationic polymer salt anda component comprising an organic solvent, a corrosion inhibitor, anorganic sulfur compound, an asphaltene inhibitor, a paraffin inhibitor,a scale inhibitor, an emulsifier, a water clarifier, a dispersant, anemulsion breaker, a gas hydrate inhibitor, a biocide, a pH modifier, asurfactant, or a combination thereof to inhibit corrosion on thesurface; or adding the compound or the composition to a fluid whichcontacts the surface to inhibit corrosion on the surface. The cationicpolymer salt can be one or more of the cationic polymer salts asdescribed herein such as compounds 1-15. The composition can be anycomposition as described herein.

The polymer salts/compositions can be used for inhibiting corrosion inoil and gas applications such as by treating a gas or liquid stream withan effective amount of a compound or composition as described herein.The compounds and compositions can be used in any industry where it isdesirable to inhibit corrosion at a surface.

The polymer salts/compositions can be used in water systems,condensate/oil systems/gas systems, or any combination thereof. Forexample, the polymer salts/compositions can be used in controlling scaleon heat exchanger surfaces.

The polymer salts/compositions can be applied to a gas or liquidproduced, or used in the production, transportation, storage, and/orseparation of crude oil or natural gas.

The polymer salts/compositions can be applied to a gas stream used orproduced in a coal-fired process, such as a coal-fired power plant.

The polymer salts/compositions can be applied to a gas or liquidproduced or used in a waste-water process, a farm, a slaughter house, aland-fill, a municipality waste-water plant, a coking coal process, or abiofuel process.

A fluid to which the polymer salts/compositions can be introduced can bean aqueous medium. The aqueous medium can comprise water, gas, andoptionally liquid hydrocarbon.

A fluid to which the polymer salts/compositions can be introduced can bea liquid hydrocarbon. The liquid hydrocarbon can be any type of liquidhydrocarbon including, but not limited to, crude oil, heavy oil,processed residual oil, bituminous oil, coker oils, coker gas oils,fluid catalytic cracker feeds, gas oil, naphtha, fluid catalyticcracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, andkerosene.

The fluid or gas can be a refined hydrocarbon product.

A fluid or gas treated with a polymer salt/composition can be at anyselected temperature, such as ambient temperature or an elevatedtemperature. The fluid (e.g., liquid hydrocarbon) or gas can be at atemperature of from about 40° C. to about 250° C. The fluid or gas canbe at a temperature of from −50° C. to 300° C., 0° C. to 200° C., 10° C.to 100° C., or 20° C. to 90° C. The fluid or gas can be at a temperatureof 22° C., 23° C., 24° C., 25° C., 26° C., 27° C., 28° C., 29° C., 30°C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37° C., 38° C., 39°C., or 40° C. The fluid or gas can be at a temperature of 85° C., 86°C., 87° C., 88° C., 89° C., 90° C., 91° C., 92° C., 93° C., 94° C., 95°C., 96° C., 97° C., 98° C., 99° C., or 100° C.

The polymer salts/compositions can be added to a fluid at various levelsof water cut. For example, the water cut can be from 0% to 100%volume/volume (v/v), from 1% to 80% v/v, or from 1% to 60% v/v. Thefluid can be an aqueous medium that contains various levels of salinity.The fluid can have a salinity of 0% to 25%, about 1% to 24%, or about10% to 25% weight/weight (w/w) total dissolved solids (TDS).

The fluid or gas in which the polymer salts/compositions are introducedcan be contained in and/or exposed to many different types ofapparatuses. For example, the fluid or gas can be contained in anapparatus that transports fluid or gas from one point to another, suchas an oil and/or gas pipeline. The apparatus can be part of an oiland/or gas refinery, such as a pipeline, a separation vessel, adehydration unit, or a gas line. The fluid can be contained in and/orexposed to an apparatus used in oil extraction and/or production, suchas a wellhead. The apparatus can be part of a coal-fired power plant.The apparatus can be a scrubber (e.g., a wet flue gas desulfurizer, aspray dry absorber, a dry sorbent injector, a spray tower, a contact orbubble tower, or the like). The apparatus can be a cargo vessel, astorage vessel, a holding tank, or a pipeline connecting the tanks,vessels, or processing units.

The polymer salts/compositions can be introduced into a fluid or gas byany appropriate method for ensuring dispersal through the fluid or gas.

The polymer salts/compositions can be added to the hydrocarbon fluidbefore the hydrocarbon fluid contacts the surface.

The polymer salts/compositions can be added at a point in a flow lineupstream from the point at which corrosion prevention and/or schmooremoval is desired.

The polymer salts/compositions can be injected using mechanicalequipment such as chemical injection pumps, piping tees, injectionfittings, atomizers, quills, and the like.

The polymer salts/compositions of the invention can be introduced withor without one or more additional polar or non-polar solvents dependingupon the application and requirements.

The polymer salts/compositions can be pumped into an oil and/or gaspipeline using an umbilical line. A capillary injection system can beused to deliver the polymer salts/compositions to a selected fluid.

A fluid to which the compositions can be introduced can be an aqueousmedium. The aqueous medium can comprise water, gas, and optionallyliquid hydrocarbon. A fluid to which the polymer salts/compositions canbe introduced can be a liquid hydrocarbon.

The polymer salts/compositions can be introduced into a liquid andmixed.

The polymer salts/compositions can be injected into a gas stream as anaqueous or non-aqueous solution, mixture, or slurry.

The fluid or gas can be passed through an absorption tower comprisingpolymer salts/compositions.

The polymer salts/compositions can be applied to a fluid or gas toprovide any selected concentration. In practice, the polymersalts/compositions are typically added to a flow line to provide aneffective treating dose of the described compounds from about 0.01 toabout 5,000 ppm. The polymer salts/compositions can be applied to afluid or gas to provide an actives concentration of about 1 parts permillion (ppm) to about 1,000,000 ppm, about 1 parts per million (ppm) toabout 100,000 ppm, or about 10 ppm to about 75,000 ppm. The polymersalts/compositions can be applied to a fluid to provide an activesconcentration of about 100 ppm to about 10,000 ppm, about 200 ppm toabout 8,000 ppm, or about 500 ppm to about 6,000 ppm. The activesconcentration means the concentration of the compounds of formula (1).

The polymer salts/compositions can be applied to a fluid or gas toprovide actives concentration of 0.1 ppm, 0.5 ppm, 1 ppm, 2 ppm, 5 ppm,10 ppm, 20 ppm, 100 ppm, 200 ppm, 500 ppm, or 1,000 ppm. The polymersalts/compositions can be applied to a fluid or gas to provide anactives concentration of 0.125 ppm, 0.25 ppm, 0.625 ppm, 1 ppm, 1.25ppm, 2.5 ppm, 5 ppm, 10 ppm, or 20 ppm. Each system can have its owndose level requirements, and the effective dose level of polymersalts/compositions to sufficiently reduce the rate of corrosion can varywith the system in which it is used.

The polymer salts/compositions can be applied continuously, in batch, ora combination thereof. The polymer salts/compositions doses can becontinuous to prevent corrosion. The polymer salts/compositions dosescan be intermittent (i.e., batch treatment) or the polymersalts/compositions doses can be continuous/maintained and/orintermittent to inhibit corrosion.

Dosage rates for continuous treatments typically range from about 10 toabout 500 ppm, or about 10 to about 200 ppm. Dosage rates for batchtreatments typically range from about 10 to about 400,000 ppm, or about10 to about 20,000 ppm. The polymer salts/compositions can be applied asa pill to a pipeline, providing a high dose (e.g., 20,000 ppm) of thecomposition.

The flow rate of a flow line in which the polymer salt/composition isused can be between 0 and 100 feet per second, or between 0.1 and 50feet per second. The polymer salts/compositions can also be formulatedwith water in order to facilitate addition to the flow line.

The surface can be a part of a wellbore or equipment used in theproduction, transportation, storage, and/or separation of a fluid suchas crude oil or natural gas.

More specifically, the surface can be a part of equipment used acoal-fired process, a waste-water process, a farm, a slaughter house, aland-fill, a municipality waste-water plant, a coking coal process, or abiofuel process. Preferably, the surface can be a part of equipment usedin the production of crude oil or natural gas.

The equipment can comprise a pipeline, a storage vessel, downholeinjection tubing, a flow line, or an injection line.

The polymer salts/compositions of the invention can be used forinhibiting corrosion in other applications.

The polymer salts/compositions are useful for corrosion inhibition ofcontainers, processing facilities, or equipment in the food service orfood processing industries. The polymer salts/compositions haveparticular value for use on food packaging materials and equipment, andespecially for cold or hot aseptic packaging. Examples of processfacilities in which the polymer salts/compositions can be employedinclude a milk line dairy, a continuous brewing system, food processinglines such as pumpable food systems and beverage lines, ware washmachines, low temperature ware wash machines, dishware, bottle washers,bottle chillers, warmers, third sink washers, processing equipment suchas tanks, vats, lines, pumps and hoses (e.g., dairy processing equipmentfor processing milk, cheese, ice cream and other dairy products), andtransportation vehicles. The polymer salts/compositions can be used toinhibit corrosion in tanks, lines, pumps, and other equipment used forthe manufacture and storage of soft drink materials, and also used inthe bottling or containers for the beverages.

The polymer salts/compositions can also be used on or in otherindustrial equipment and in other industrial process streams such asheaters, cooling towers, boilers, retort waters, rinse waters, asepticpackaging wash waters, and the like. The polymer salts/compositions canbe used to treat surfaces in recreational waters such as in pools, spas,recreational flumes and water slides, fountains, and the like.

The polymer salts/compositions can be used to inhibit the corrosion ofmetal surfaces contacted with cleaners in surfaces found in janitorialand/or housekeeping applications, food processing equipment and/or plantapplications, and in laundry applications. For example, the corrosion ofwashers, such as tunnel washers for washing textiles, can be inhibitedaccording to methods disclosed herein.

The polymer salts/compositions can be used or applied in combinationwith low temperature dish and/or warewash sanitizing final rinse, toiletbowl cleaners, and laundry bleaches. The compounds, compositions andmethods can be used to treat metal surfaces, such as ware, cleanedand/or sanitized with corrosive sources.

The compounds, compositions and methods disclosed herein protectsurfaces from corrosion caused by hypochlorite bleach. A method caninclude providing the corrosion inhibitor polymer salts/compositions toa surface treated with a hypochlorite solution in order to inhibitcorrosion caused by the hypochlorite solution. The method can includepreparing an aqueous use composition of the present corrosion inhibitorcomposition. The method can further include contacting a surface, suchas a hard metal surface, in need of corrosion inhibition due to contactwith a hypochlorite solution.

The polymer salts/compositions can be dispensed in any suitable methodgenerally known by one skilled in the art. For example, a spray-typedispenser can be used, such as that disclosed in U.S. Pat. Nos.4,826,661, 4,690,305, 4,687,121, 4,426,362 and in U.S. Pat. Nos. Re32,763 and 32,818, the disclosures of which are incorporated byreference herein. A spray-type dispenser functions by impinging a waterspray upon an exposed surface of a composition to dissolve a portion ofthe composition, and then immediately directing the concentrate solutionincluding the composition out of the dispenser to a storage reservoir ordirectly to a point of use.

The polymer salts/compositions can be dispensed by immersing eitherintermittently or continuously in water. The composition can thendissolve, for example, at a controlled or predetermined rate. The ratecan be effective to maintain a concentration of dissolved agent that iseffective for use according to the methods disclosed herein.

EXAMPLES

The following non-limiting examples are provided to further illustratevarious aspects of the present disclosure. All chemicals were used asreceived from the supplier unless otherwise noted.

NMR samples of the cationic polymer salts were prepared in D₂O. Allspectra were acquired at 25° C. Quantitative proton (¹H) and carbon(¹³C) were acquired using a single-pulse sequence implemented on anAGILENT 500 MHz spectrometer equipped with a 10 mm broad-band probe forcarbon or a 5 mm two-channel probe for proton with Z-gradient. ¹Hspectra were acquired with 4-8 scans. ¹³C spectra were acquired with400-500 scans. Data were processed and analyzed using MestReNova v. 9(Mestrelab, Spain).

The chemical shifts (ppm) are reported relative to TMS(tetramethylsilane) using the residual solvent peak as reference unlessotherwise noted. The following abbreviations are used to express themultiplicities: s=singlet; d=doublet; t=triplet; q=quartet; m=multiplet;br=broad.

Mass spectroscopy of the cationic surfactants was conducted on a QEXACTIVE ORBITRAP high resolution mass spectrometer (Thermo FisherScientific) equipped with a quadrupole as an ion filter and with anelectrospray ionization (ESI) source. Surfactant samples were diluted toabout 100 ppm and then injected into the mass spectrometer by infusionat the flow rate of 10 μL/minute. Spectra were acquired in positive ESImode; scan range: 50-750 m/z; resolution: 140 k; AGC target: 3⁶; sheathgas flow rate: 2 (arbitrary unit); auxiliary gas flow rate: 0 (arbitraryunit); spray voltage: 2.5 kV; capillary temperature: 150° C.; auxiliarygas heater temperature: 30° C.; and S-Len RF level: 50. Data wereacquired and analyzed by XCALIBUR and FREESTYLE software (Thermo FisherScientific).

Example 1: Synthesis of Multiple Quaternary Cationic Surfactants withMethyl Groups

Diethylenetriamine (DETA, 10.32 grams, 0.10 mol) and3-chloro-2-hydroxypropyl trimethylammonium chloride (156.7 grams, 60.0%,0.50 mol, (Sigma-Aldrich) were added to a 500 mL four-neck round bottomflask equipped with a mechanical stirrer, a thermometer, a temperaturecontroller, a condenser, and an addition funnel. The reaction mixturewas stirred and gently heated to 60° C. The pH value of the reaction wascontinuously monitored. Sodium hydroxide (50% aqueous solution) wasslowly added to the reaction flask and the temperature was held constantat 60° C. The pH value of reaction solution was measured and was heldconstant above 7.5. The reaction temperature was raised to 85° C. andheld constant for 5 hours. The reaction scheme is as follows wherein R₁,R₂ and R₃ are methyl and n is 1:

¹³C NMR (500 MHz, D₂O, 25° C.) spectra showed the chemical shifts at44-46 ppm and 58-59.3 ppm which were assigned to the reacted DETA. Theresonance signal at 47.5 ppm represents the chlorinated methylene inunreacted 3-chloro-2-hydroxypropyl trimethylammonium chloride. The totalamount of 3-chloro-2-hydroxypropyl trimethylammonium chloride wasdetermined based on the sharp signal at 54.5 ppm from the methyl groups.The average charge per DETA was 4.8, consistent with theoretical valuesof 5 charges. MS (ESI): calc. [M-2Cl⁻]²⁺ 394.275, found 394.278; calc.[M-3Cl⁻]³⁺ 251.193, found 251.195; calc. [M-4Cl⁻]⁴⁺ 179.655, found179.654; calc. [M-5Cl⁻]⁵⁺ 136.73, found 136.73.

Example 2: Synthesis of Multiple Quaternary Cationic Surfactants withLauryl Groups

Multiple quaternary cationic surfactants with lauryl chains weresynthesized by reacting diethylenetriamine (DETA) and3-chloro-2-hydroxypropyl-dodecyl-dimethylammonium chloride (QUAB 342™from Quab Chemicals, Saddle Brook, N.J.). Diethylenetriamine (5.16grams, 0.05 mol) and 3-chloro-2-hydroxypropyl-dodecyl-dimethylammoniumchloride (222.66 grams, 38.4 wt. %, 0.25 mol) were charged to a 500 mLfour-neck round bottom flask equipped with a mechanical stirrer, athermometer, a temperature controller, a condenser, and an additionfunnel. The reaction mixture was stirred and gently heated to 60° C. ThepH value of the reaction was continuously monitored. Sodium hydroxide(50% aqueous solution) was slowly added to the reaction flask and thetemperature was held constant at 60° C. The pH value of reactionsolution was measured and was held constant above 7.5. The reactiontemperature was raised to 85° C. and held constant for 5 hours.

The mass spectroscopy data showed that the reaction product contained amixture of 2 quaternary −2 dimethyl dodecyl ammonium chlorides (MS(ESI): calc. [M-2Cl⁻]²⁺ 321.83, found 321.83); 3 quaternary −3 dimethyldodecyl ammonium chlorides (MS (ESI): calc. [M-Cl⁻]⁺ 983.89, found983.89; calc. [M-2Cl⁻]²⁺ 474.46, found 474.46; 4 quaternary −4 dimethyldodecyl ammonium chlorides (MS (ESI): calc. [M-Cl⁻]⁺ 1289.14, found1289.13, calc. [M-2Cl⁻]²⁺ 627.08, found 627.08; calc. [M-3Cl⁻]³⁺ 406.40,found 406.40; calc. [M-4Cl⁻]⁴⁺ 296.06, found 296.06); and 5 quaternary−5 dimethyl dodecyl ammonium chlorides (MS (ESI): calc. [M-2Cl⁻]²⁺779.71, found 779.71; calc. [M-3Cl⁻]³⁺ 508.15, found 508.48; calc.[M-4Cl⁻]⁴⁺ 372.37, found 372.37). Surface tension, 63.63 mN/m @0.050 wt% aqueous solution.

Example 3: Synthesis of Multiple Quaternary Cationic Surfactants withDifferent Alkyl Chains

A five-quaternary cationic surfactant was synthesized by reactingdiethylene triamine (DETA, 10.32 grams, 0.10 mol) and3-chloro-2-hydroxypropyl trimethylammonium chloride (62.7 grams, 60.0%0.20 0 mol) and 3-chloro-2-hydroxypropyl-dimethyldodecylammoniumchloride (267.2 grams, 38.4 wt. %, 0.30 mol) (QUAB 342™) using theprocedure described in Example 1.

Alternatively, the synthesis can be conducted using a mixture of3-chloro-2-hydroxypropyl trimethylammonium chloride and3-chloro-2-hydroxypropyl-dimethyloctadecylammonium chloride withdifferent molar ratios; however a total of 5 moles of trialkylammoniumchloride was held constant.

A six-quaternary cationic surfactant was synthesized by reactingtriethylene tetraamine (TETA, 12.2 grams, 60 wt. %, 0.05 moles) and3-chloro-2-hydroxypropyldimethyloctadecylammonium chloride (336.3 grams,38.0%, 0.30 mol; QUAB 426™ from Quab Chemicals, Saddle Brook, N.J.) inpropylene glycol (PP425, 69.9 grams) using the procedure described inExample 1.

It was determined that varying the solvents between a mixture ofwater/propanediol and water/propanediol/PP425 or water/hexylene glycolachieved a homogenous phase during the reaction. Further, it was foundthat propanediol and propylene glycol increased the water solubility ofmultiple cationic surfactants with long alkyl chains.

Compound 1 was synthesized using diethylenetriamine (1 mol),(3-chloro-2-hydroxypropyl) lauryl dimethylammonium chloride (4 mol), and(3-chloro-2-hydroxypropyl)trimethylammonium chloride (1 mol). Massspectrometry confirmed synthesis of Compound 1: calc. [M-2Cl⁻]²⁺ 702.62,found 703.62; calc. [M-3Cl⁻]³⁺ 456.76, found 457.09.

Compound 2 was synthesized using diethylenetriamine (1 mol),(3-chloro-2-hydroxypropyl)lauryl dimethylammonium chloride (3 mol), and(3-chloro-2-hydroxypropyl)trimethylammonium chloride (2 mol). Massspectrometry confirmed synthesis of Compound 2: calc. [M-2Cl⁻]²⁺ 625.54,found 626.53; calc. [M-3Cl⁻]³⁺ 405.37, found 405.7; calc. [M-4Cl⁼]⁴⁺295.28, found 295.28.

Compound 3 was synthesized using diethylenetriamine (1 mol) and(3-chloro-2-hydroxypropyl)lauryl dimethylammonium chloride (5 mol). Massspectrometry confirmed synthesis of Compound 3: calc. [M-2Cl⁻]²⁺ 779.71,found 779.71; calc. [M-3Cl⁻]³⁺ 508.15, found 508.48; calc. [M-4Cl⁻]⁴⁺372.37, found 372.37.

Compound 4 was synthesized using diethylenetriamine (1 mol),(3-chloro-2-hydroxypropyl)octadecyl dimethylammonium chloride (3 mol),and (3-chloro-2-hydroxypropyl)trimethylammonium chloride (2 mol).

Compound 5 and 6 were synthesized similarly to Compounds 1-3, asdescribed above. Mass spectrometry confirmed synthesis of Compound 5:calc. [M-2Cl⁻]²⁺ 548.45, found 549.45; calc. [M-3Cl³¹]³⁺ 353.98, found354.64; calc. [M-4Cl⁻]⁴⁺ 256.74, found 256.74. Mass spectrometryconfirmed synthesis of Compound 6: [M-5Cl⁻]⁵⁺ 167.56, found 167.56.

Compounds 7-12 were synthesized in a similar manner as compound 4described above. Different ratios of reactants yielded differentproportions of long chain alkyl groups in the cationic polymer.

Various multiple cationic surfactants were synthesized using theabove-mentioned synthetic scheme, e.g. DETA, TETA,3-chloro-2-hydroxypropyl trimethylammonium chloride (QUAT 188™ cationicmonomer from Dow Chemical Company of Midland, Mich.) and QUAB 426™reactants, and the products are summarized in Table 1, below. Regardingthe structures reported in Table 1, “5Q-1 Stearyl (C18)/4 trimethylquats” means that the product has 5 total quaternary groups (5Q) ofwhich 1 quat group had R₁ and R₂ as methyl and R₃ as stearyl, and 4 quatgroups had R₁, R₂ and R₃ as methyl, and n=1. Likewise, “5Q-2 Stearyl(C18)/3 trimethyl quats” means that the product has 5 total quaternarygroups (5Q) of which 2 quat groups had R₁ and R₂ as methyl and R₃ asstearyl, and 3 quat groups had R₁, R₂ and R₃ as methyl, and n=1. “5Q-3Stearyl (C18)/2 trimethyl quats” means that the product has 5 totalquaternary groups (5Q) of which 3 quat groups had R₁ and R₂ as methyland R₃ as stearyl, and 2 quat groups had R₁, R₂ and R₃ as methyl, andn=1. “5Q-4 Stearyl (C18)/1 trimethyl quat” means that the product has 5total quaternary groups (5Q) of which 4 quat groups had R₁ and R₂ asmethyl and R₃ as stearyl, and 1 quat group had R₁, R₂ and R₃ as methyl,and n=1. “5Q-5 Stearyl (C18)” means that the product has 5 totalquaternary groups (5Q) of which 5 quat groups had R₁ and R₂ as methyland R₃ as stearyl, and n=1. “6Q-6 Stearyl(C18)” means that the producthas 6 total quaternary groups (6Q) of which 6 quat groups had R₁ and R₂as methyl and R₃ as stearyl, and n=2.

TABLE 1 Physical properties of multiple quaternary cationic surfactantsCompound Ratio of QUAB Active, wt % No. Structure Polyamine 426/QUAT188Solvent Calculated, % Measured, % 7 5Q-1 DETA 1/4 Water/ 51.47 52.58Stearyl Propanediol (C18)/4 trimethyl quats 9 5Q-2 DETA 2/3 Water/ 46.5451.3 Stearyl Propanediol (C18)/3 trimethyl quats 10 5Q-3 DETA 3/2 Water/43.41 61.77 Stearyl Propanediol (C18)/2 trimethyl quats 11 5Q-4 DETA 4/1Water/ 33.68 62.88 Stearyl Propanediol/ (C18)/1 PP425 trimethyl quat 125Q-5 DETA 5/0 Water/ 33.74 53.99 Stearyl Propanediol/ (C18) PP425 136Q-6 TETA 6/0 Water/ 33.28 49.40 Stearyl Propanediol/ (C18) PP425

The mass spectra of Compound 9 showed that the reaction productcontained a mixture of 2-C18/3-Trimethyl (MS (ESI): calc. [M-2Cl⁻]²⁺632.545; found 632.5423; calc. [M-3Cl⁻]³⁺ 410.04, found 410.038; calc.[M-4Cl⁻]⁴⁺ 298.7875, found 298.786; calc. [M-5Cl⁻]⁵⁺ 232.036, found232.210); 2-C16/3-Trimethyl (MS (ESI): calc. [M-2Cl⁻]²⁺ 604.51; found604.51 calc. [M-3Cl⁻]³⁺ 391.35, found 391.35; calc. [M-4Cl⁻]⁴⁺ 284.77,found 284.77; calc. [M-5Cl⁻]⁵⁺ 220.824, found 220.555);1-C18/1-C16/3-Trimethyl (MS (ESI): calc. [M-2Cl⁻]²⁺ 618.525; found618.5266; calc. [M-3Cl⁻]³⁺ 400.697, found 400.694; calc. [M-4Cl⁻]⁴⁺291.78, found 291.778; calc. [M-5Cl⁻]⁵⁺ 226.43, found 226.429);1-C18/4-Trimethyl (MS (ESI): calc. [M-2Cl⁻]²⁺ 513.41; found 513.4098;calc. [M-3Cl⁻]³⁺ 330.62, found 330.6166; calc. [M-4Cl⁻]⁴⁺ 239.22, found239.2202; calc. [M-5Cl⁻]⁵⁺ 184.38, found 184.3823); and1-C16/4-Trimethyl (MS (ESI): calc. [M-2Cl⁻]²⁺ 449.395; found 449.4368;calc. [M-3Cl⁻]³⁺ 321.27, found 321.2728; calc. [M-4Cl⁻]⁴⁺ 232.21, found232.212; calc. [M-5Cl⁻]⁵⁺ 178.776, found 178.776).

Example 4: Surface Tension Measurements and Critical MicelleConcentrations (CMC) Calculations

Surface tension measurements were conducted on a Tracker tensiometer(Teclis Instruments) at room temperature. Various concentrations ofsurfactant solutions were prepared and measurements were conducted.

The surface tension as a function of concentration of the cationicsurfactant samples were measured and are listed in Table 2, where NTmeans not tested.

TABLE 2 Summary of surface tensions of various cationic surfactantsamples Concentration (%) 7 9 10 11 12 13 0.010 73.70 73.11 70.99 63.5263.16 63.28 0.025 72.05 69.16 61.99 60.01 55.77 59.04 0.050 64.84 60.7757.33 56.35 51.89 55.36 0.100 60.93 54.69 52.64 53.23 49.42 52.65 0.20057.12 52.05 50.58 50.16 47.02 50.31 0.500 55.13 50.09 47.92 47.38 45.0248.02 1.000 NT 49.38 47.48 46.58 44.22 47.78 1.500 NT NT NT NT 43.46 NT2.000 NT NT NT NT 42.97 NT

Surface tension of various cationic surfactant samples is also showngraphically in FIG. 1.

Example 5: Synthesis of Multiple Quaternary Cationic Surfactants Basedon a Reaction of a Polyalkyleneimine and a Substituted Alkyl TrialkylQuaternary Ammonium Salt

Polyethyleneimines (Lupasol G20 (50 wt % solution), 20 grams, 0.2204 mol—NH—) and 3-chloro-2-hydroxypropyl trimethylammonium chloride (69.06grams, 60.0%, 0.2204 mol, (Sigma-Aldrich) were added to a 500 mLfour-neck round bottom flask equipped with a mechanical stirrer, athermometer, a temperature controller, a condenser, and an additionfunnel. The reaction mixture was stirred and gently heated to 60° C. ThepH value of the reaction was continuously monitored. Sodium hydroxide(50% aqueous solution) was slowly added to the reaction flask and thetemperature was held constant at 60° C. The pH value of reactionsolution was measured and was held constant above 7.5. The reactiontemperature was raised to 85° C. and held constant for 5 hours. Compound14 depicted below is a depiction of a generalized reaction product. Thestructure below depicts that all of the secondary and primary amines inthe polyethyleneimine react with the 3-chloro-2-hydroxypropyltrimethylammonium chloride so that no secondary amines remain. There maybe some amines that do not completely react leaving some secondaryamines in the cationic polymer salt.

Multiple quaternary cationic surfactants with stearyl chains weresynthesized by reacting polyethyleneimines branched (Sigma-Aldrich) with3-chloro-2-hydroxypropyl-stearyldimethylammonium chloride (QUAB 426™from Quab Chemicals, Saddle Brook, N.J.) and 3-chloro-2-hydroxypropyltrimethylammonium chloride (Sigma-Aldrich). Polyethyleneimines (40.0grams (50%), 0.4206 mol —NH—) and3-chloro-2-hydroxypropyl-stearyldimethylammonium chloride (47.15 grams,38.5 wt. %, 0.0426 mol) and 3-chloro-2-hydroxypropyl trimethylammoniumchloride (118.6 grams, (60%), 0.3785 mol) were charged to a 500 mLfour-neck round bottom flask equipped with a mechanical stirrer, athermometer, a temperature controller, a condenser, and an additionfunnel. The reaction mixture was stirred and gently heated to 60° C. ThepH value of the reaction was continuously monitored. Sodium hydroxide(50% aqueous solution) was slowly added to the reaction flask and thetemperature was held constant at 60° C. The pH value of reactionsolution was measured and was held constant above 7.5. The reactiontemperature was raised to 85° C. and held constant for 5 hours. Surfacetension, 41.55 mN/m @0.050 wt % aqueous solution. Compound 15 shows ageneralized reaction product. Like Compound 14, there may be somesecondary amines present if the reaction did not proceed to completion.

Polymeric quaternary compounds were synthesized according to theprocedures described above to produce Compound 15 and Compound 16.Compound 16 had a weight average molecular weight of about 1300 gm/molas measured by gel permeation chromatography. Compound 15 had a weightaverage molecular weight of about 25,000 gm/mol as measured by gelpermeation chromatography. The variable “p” may range from about 10 toabout 10⁵.

Example 6: Antimicrobial Effects of Cationic Polymer Salts

Antimicrobial efficiency of the synthesized compounds was tested using anon-oxidative antimicrobial efficiency test procedure according to ASTMmethod for microbiocide efficiency in cooling water (E645-02a, 2005).The bacteria used in the efficacy testing comprised a mixture of aerobicpopulations from more than 30 cooling systems in North America. Thespecific species were not identified. Those species were grown on R₂Aagar.

In one experiment, various concentrations (0 ppm, 5 ppm, 10 ppm, 20 ppm,30 ppm, 40 ppm, and 50 ppm) of Compound 1 were applied to bacteria inwater. The log 10 concentration in colony forming units (CFU/ml) wasmeasured at four time points (0 min, 60 min, 240 min, and 1440 min).FIGS. 1 and 2 show that at a concentration of 5 ppm a single log 10reduction was achieved. At about 20 ppm, a five log 10 reduction wasobserved at about 60 min, 240 min, and 1440 min.

The microbial activity of Compounds 1-4 at a concentration of 50 ppm wastested according to the same procedure described above. FIG. 3 showsthat all the compounds show significant reduction in CFUs after 60 mincontact time. At about 5 ppm, Compound 2 showed some antimicrobialactivity showing a single log 10 reduction in CFUs.

The antimicrobial activity of Compound 4 was tested using the sameprocedures as described above. FIGS. 4 and 5 show significantantimicrobial activity at the tested concentrations.

Example 7: Cationic Polymer Salt Effect on Spores and Thermophiles

The effect of the compounds on bacterial spores or thermophiles was alsotested. Compounds 1 and 4 were incubated separately with spores orthermophiles at a concentration of about 20 ppm, and the reduction inconcentration was measured at four time points (See Table 3).

TABLE 3 Summary of anti-spore and anti-thermophile activity Com- Com-Com- Com- Contact Control pound pound pound pound Time (Log 1 (Log 1 Log4 (Log 4 Log (min) cfu/ml) cfu/ml) Reduction cfu/ml) Reduction 0 2.492.41 0.08 2.53 −0.04 60 2.34 1.85 0.5 1.6 0.74 240 2.48 1.48 1.0 0.002.48 1440 2.53 1.48 1.05 1.78 0.75

Example 8: Antimicrobial Efficacy of Single Quaternary Compounds andMulti-Quaternary Cationic Polymers

Biofilm reduction experiments were conducted to test the efficacy ofmulti-quaternary cationic polymers compared to single quaternarycompounds. Two different compositions were prepared containing singlequaternary compounds: a composition (Single Quat 1) comprising about 50%by weight bisoctyl dimethyl ammonium chloride (CAS #5538-94-3) and about5-10% by weight glycerin; and a composition (Single Quat 2) comprisingabout 50% by weight didecyl-dimethyl ammonium chloride (CAS #7173-51-5)and about 10-30% by weight ethanol. The test bacteria comprised acollection of aerobic bacteria from 30 water samples in cooling towersacross North America. Different concentrations of cationic polymer saltsand single quaternary compounds were tested ranging from about 0.8 ppmto about 1000 ppm. Using the biofilm inhibition test protocols, theabsorbed stains were extracted and absorbance was measured at 590 nm.The biofilm reduction was calculated by comparing the absorbance oftreated vs untreated controls, then averaged over six replicates.

Compounds 7 and 9 were compared the Single Quat 2 composition describedabove. Tables 4 and 5 show that at concentrations as low as about 12 ppmthat Compound 7 reduced biofilms to a greater extent than the SingleQuat 2 composition. Compound 7 also had biofilm reduction of about 12 toabout 65% in from about 0.8 ppm to about ppm concentration range.Compound 9 achieved greater than 95% reduction in biofilm formation atconcentrations about 100 ppm. The compounds show significant advantagesover traditional products.

TABLE 4 Biofilm reduction of Compound 7 compared to Single Quat 2 (Comp.7 - Single Quat 2)*100 Active Conc. Single Quat 2 Compound 7 Single Quat2 ppm % % % 1000.0 60.1 98.4 63.7 500.0 92.0 97.8 6.3 250.0 84.2 97.115.3 125.0 −6.8 96.6 1517.3 100.0 −15.6 79.3 608.5 62.0 65.4 96.6 47.650.0 80.4 93.0 15.7 31.0 81.6 94.7 16.0 25.0 80.3 90.6 12.9 16.0 81.790.6 10.9 12.0 52.5 65.1 24.2 8.0 69.3 54.9 −20.8 6.0 8.0 23.5 195.0 3.034.5 46.7 35.5 1.6 −5.7 12.7 321.3 0.8 11.1 22.9 106.8

TABLE 5 Biofilm reduction of Compound 9 compared to Single Quat 2 (Comp.9 - Single Quat 2)*100 Active Conc. Single Quat 2 Compound 9 Single Quat2 ppm % % % 1000.0 74.7 99.6 33.5 500.0 80.5 99.6 23.7 250.0 64.1 99.555.3 125.0 52.4 98.9 88.6 100.0 68.6 97.3 41.9 62.0 91.1 90.7 −0.4 50.092.2 77.6 −15.9 31.0 95.4 46.9 −50.8 25.0 91.3 76.8 −15.9 16.0 93.5 79.0−15.5 12.0 81.6 70.9 −13.2 8.0 68.5 62.6 −8.6 6.0 51.1 45.4 −11.1 3.072.5 41.2 −43.2 1.6 39.7 35.9 −9.6 0.8 −9.6 20.5 314.7

Example 9: Biofilm Reduction Using Polymeric Quats Compared to SingleQuat 2

A biofilm assay was performed using a modified version of ASTM E2799-11.Single Quat 2 was compared to Compound 15. Table 6 shows the percentchange in the biofilm compared the Single Quat 2. FIG. 7 and FIG. 8 showa graphical representation of biofilm reduction of Compound 15 comparedto Single Quat 2 and Compound 16.

TABLE 6 Biofilm reduction of Compound 15 compared to Single Quat 2(Comp. 15 - Single Quat 2)*100 Active Conc. Single Quat 2 Compound 15Single Quat 2 ppm % % % 1000.0 68.0 99.6 46.5 500.0 83.2 99.3 19.4 250.069.2 94.8 37.1 125.0 44.1 84.4 91.4 100.0 45.9 93.8 104.2 62.0 73.8 53.8−27.1 50.0 89.8 85.8 −4.5 31.0 79.4 62.6 −21.1 25.0 92.4 72.8 −21.2 16.086.7 52.7 −39.2 12.0 86.1 55.5 −35.6 8.0 71.0 18.0 −74.6 6.0 8.2 25.9217.6 3.0 65.3 12.3 −81.2 2 17.8 12.7 −28.7 1 −30.0 −0.1 −99.5

Single Quat 2 was compared to Compound 16 in a biofilm assay. Table 7shows the percent change in the biofilm compared the Single Quat 2. FIG.7 and FIG. 8 show a graphical representation of biofilm reduction ofCompound 16 compared to Single Quat 2 and Compound 15.

TABLE 7 Biofilm reduction of Compound 16 compared to Single Quat 2(Comp. 16 - Single Quat 2)*100 Active Conc. Single Quat 2 Compound 16Single Quat 2 ppm % % % 1000.0 74.7 93.3 25.0 500.0 80.5 84.8 5.3 250.064.1 76.7 19.7 125.0 52.4 64.4 22.8 100.0 68.6 74.3 8.4 62.0 91.1 30.4−66.6 50.0 92.2 45.2 −51.0 31.0 95.4 −6.0 −106.3 25.0 91.3 25.9 −71.616.0 93.5 −2.7 −102.9 12.0 81.6 14.4 −82.3 8.0 68.5 −29.3 −142.8 6.051.1 1.9 −96.3 3.0 72.5 −1.7 −102.3 1.6 39.7 1.4 −96.5 0.8 −9.6 −10.0−4.9

Example 10: Corrosion Bubble Cell Tests of Pentaquaternary CationicPolymer Salts

Cationic polymer salts were evaluated for corrosion performance ascompared to a C₁₂-C₁₈ alkyl dimethyl benzyl ammonium chloride via abubble test procedure. The bubble test simulates low flow areas wherelittle or no mixing of water and oil occurs. The test was conductedusing brine (80% of the brine being 3% sodium chloride brine and 20% ofthe brine being a hydrocarbon containing 75% LVT-200 kerosene oil and25% xylene). The brine was placed into kettles and purged with carbondioxide. The brine was continually purged with carbon dioxide tosaturate the brine prior to starting the test. After the test began, thetest cell was blanketed with carbon dioxide one hour prior to electrodeinsertion and through the duration of the test to maintain saturation.The kettles were stirred at 150 revolutions per minute (rpm) for theduration of the test to maintain thermal equilibrium at 80° C. Thecorrosion rate was measured by Linear Polarization Resistance (LPR)techniques. The working electrode used was carbon steel. The counter andreference electrodes were both 1018 carbon steel. The electrodes wereall cleaned and polished prior to testing. Data were collected for threehours before 20 ppm of each of the compositions (containing 2 ppm ofeach of various pentaquaternary cationic polymer salts or thecomparative C₁₂-C₁₈ alkyl dimethyl benzyl ammonium chloride and 1%2-mercaptoethanol (2ME) as synergist in an organic solvent) was dosedinto its respective cell. Data were collected overnight. A lowconcentration of the compositions was used to differentiate between thecompositions.

The results of the bubble test are shown in Table 8, wherein ppm isparts per million, CI is corrosion inhibitor, mpy is mils per year, andthe Compound No. is as listed in Table 1 and/or depicted in Example 3.

TABLE 8 Bubble test results Average Baseline Inhibited Cationic Dosageof Corrosion Rate Corrosion Rate 15 Polymer Salt or Cationic BeforeCationic h After Cationic Comparative Polymer Salt or Polymer Salt orPolymer Salt or Cationic Compound Compound Addition Compound Addition %Compound (ppm) Synergist (mpy) (mpy) Protection None 0 None 260 500 −92C₁₂-C₁₈ alkyl 2 1% 2ME 236 147 38 dimethyl benzyl ammonium chloride(Comparative) Compound 1 (4 2 1% 2ME 223 130 42 lauryl dimethyl & 1trimethyl quats) Compound 7 (1 2 1% 2ME 251 90 64 stearyl dimethyl & 1trimethyl quats) Compound 9 (2 2 1% 2ME 226 90 60 stearyl dimethyl & 3trimethyl quats) Compound 11 (4 2 1% 2ME 228 55 76 stearyl dimethyl & 1trimethyl quat) Compound 12 (5 2 1% 2ME 255 115 55 stearyl dimethylquats)

Example 11: Corrosion Bubble Cell Tests of Hexaquaternary CationicPolymer Salts

Corrosion bubble cell tests were performed according to the method ofExample A1 to evaluate a hexaquaternary cationic polymer salt forcorrosion performance as compared to a C₁₂-C₁₈ alkyl dimethyl benzylammonium chloride. Data were collected for three hours before 20 ppm ofeach of the compositions (containing 2 ppm of a hexaquaternary cationicpolymer salt or the comparative C₁₂-C₁₈ alkyl dimethyl benzyl ammoniumchloride and 1% 2ME as synergist in an organic solvent) was dosed intoits respective cell. Data were collected overnight. A low concentrationof the compositions was used to differentiate between the compositions.

The results of the bubble test are shown in Table 9, wherein ppm isparts per million, CI is corrosion inhibitor, mpy is mils per year, andthe Compound No. is as listed in Table 1 and/or depicted in Example 3.

TABLE 9 Bubble test results Average Baseline Inhibited Cationic Dosageof Corrosion Rate Corrosion Rate 15 Polymer Salt or Cationic BeforeCationic h After Cationic Comparative Polymer Salt or Polymer Salt orPolymer Salt or Cationic Compound Compound Addition Compound Addition %Compound (ppm) Synergist (mpy) (mpy) Protection None 0 None 260 500 −92C₁₂-C₁₈ alkyl 2 1% 2ME 236 147 38 dimethyl benzyl ammonium chloride(Comparative) Compound 13 (6 2 1% 2ME 239 114 52 stearyl dimethyl quats)

Example 12: Corrosion Bubble Cell Tests of Polyethyleneimine-BasedCationic Polymer Salts

Cationic polymer salts were evaluated for corrosion performance ascompared to a C₁₂-C₁₈ alkyl dimethyl benzyl ammonium chloride via abubble test procedure. The bubble test simulates low flow areas wherelittle or no mixing of water and oil occurs. The test was conductedusing brine (80% of the brine being 3% sodium chloride brine and 20% ofthe brine being a hydrocarbon containing 75% LVT-200 kerosene oil and25% xylene). The brine was placed into kettles and purged with carbondioxide. The brine was continually purged with carbon dioxide tosaturate the brine prior to starting the test. After the test began, thetest cell was blanketed with carbon dioxide one hour prior to electrodeinsertion and through the duration of the test to maintain saturation.The kettles were stirred at 150 revolutions per minute (rpm) for theduration of the test to maintain thermal equilibrium at 80° C. Thecorrosion rate was measured by Linear Polarization Resistance (LPR)techniques. The working electrode used was carbon steel. The counter andreference electrodes were both 1018 carbon steel. The electrodes wereall cleaned and polished prior to testing. Data were collected for sixhours before 20 ppm of each of the compositions (containing 2 ppm ofeach of various polyethyleneimine-based cationic polymer salts or thecomparative C₁₂-C₁₈ alkyl dimethyl benzyl ammonium chloride and 1%2-mercaptoethanol (2ME) as synergist in an organic solvent) was dosedinto its respective cell. However, for the comparative composition, datawas only collected three hours before addition of the compositions. Datawere collected overnight. A low concentration of the compositions wasused to differentiate between the compositions.

The results of the bubble test are shown in Table 10, wherein ppm isparts per million, CI is corrosion inhibitor, mpy is mils per year, andthe Compound No. is as depicted in Example 5.

TABLE 10 Bubble test results Average Baseline Inhibited Cationic Dosageof Corrosion Rate Corrosion Rate 15 Polymer Salt or Cationic BeforeCationic h After Cationic Comparative Polymer Salt or Polymer Salt orPolymer Salt or Cationic Compound Compound Addition Compound Addition %Compound (ppm) Synergist (mpy) (mpy) Protection None 0 None 260 500 −92C₁₂-C₁₈ alkyl 2 1% 2ME 236 147 38 dimethyl benzyl ammonium chloride(Comparative) Compound 14 2 1% 2ME 257 138 46 Compound 15 2 1% 2ME 255134 48

It is expected that the addition of more stearyl groups to the Compound15 will further reduce the corrosion rate and provide increasedprotection as compared to Compound 15.

Any composition disclosed herein may comprise, consist of, or consistessentially of any of the compounds/components disclosed herein. Inaccordance with the present disclosure, the phrases “consist essentiallyof,” “consists essentially of,” “consisting essentially of,” and thelike limit the scope of a claim to the specified materials or steps andthose materials or steps that do not materially affect the basic andnovel characteristic(s) of the claimed invention.

As used herein, the term “about” refers to the cited value being withinthe errors arising from the standard deviation found in their respectivetesting measurements, and if those errors cannot be determined, then“about” refers to within 10% of the cited value.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While this invention may be embodied in many differentforms, there are described in detail herein specific preferredembodiments of the invention. The present disclosure is anexemplification of the principles of the invention and is not intendedto limit the invention to the particular embodiments illustrated. Inaddition, unless expressly stated to the contrary, use of the term “a”is intended to include “at least one” or “one or more.” For example, “asurfactant” is intended to include “at least one surfactant” or “one ormore surfactants.”

Any ranges given either in absolute terms or in approximate terms areintended to encompass both, and any definitions used herein are intendedto be clarifying and not limiting. Notwithstanding that the numericalranges and parameters setting forth the broad scope of the invention areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contains certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.Moreover, all ranges disclosed herein are to be understood to encompassany and all sub-ranges (including all fractional and whole values)subsumed therein.

Furthermore, the invention encompasses any and all possible combinationsof some or all of the various embodiments described herein. It shouldalso be understood that various changes and modifications to thepresently preferred embodiments described herein will be apparent tothose skilled in the art. Such changes and modifications can be madewithout departing from the spirit and scope of the invention and withoutdiminishing its intended advantages. It is therefore intended that suchchanges and modifications be covered by the appended claims.

What is claimed is:
 1. A method of inhibiting corrosion on a surface,the method comprising: contacting the surface with a cationic polymersalt to inhibit corrosion on the surface; or adding the cationic polymersalt to a fluid which contacts the surface to inhibit corrosion on thesurface, wherein the cationic polymer salt comprises a reaction productderived from a reaction of a polyamine or a polyalkyleneimine and asubstituted alkyl trialkyl quaternary ammonium salt of formula (I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with a hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl; wherein any one of the following: (A) the cationic polymer salthas no substitutions within its main chain, no alkyl-quaternizedammonium within its main chain, and comprises at least 4 quaternaryammonium groups; or (B) the cationic polymer salt has one or moreterminal tertiary amine groups having the formula (IV):

wherein R₁₁ is R₁ without the X⁻ end group, and either: the polymer salthas no substitutions within its main chain or at least 1 of R₂, R₃, andR₄ is a C₉-C₂₂ alkyl group; or (C) R₂ and R₃ are C₆-C₂₂ alkyl or C₇-C₂₂arylalkyl and R₄ is methyl.
 2. A method of inhibiting corrosion on asurface, the method comprising: contacting the surface with a cationicpolymer salt or a composition comprising the cationic polymer salt and acomponent comprising an organic solvent, a corrosion inhibitor, anorganic sulfur compound, an asphaltene inhibitor, a paraffin inhibitor,a scale inhibitor, an emulsifier, a water clarifier, a dispersant, anemulsion breaker, a gas hydrate inhibitor, a biocide, a pH modifier, asurfactant, or a combination thereof to inhibit corrosion on thesurface; or adding the cationic polymer salt or the composition to afluid which contacts the surface to inhibit corrosion on the surface,wherein either: (i) the cationic polymer salt comprises a reactionproduct derived from a reaction of a polyamine, an alkyleneimine, or apolyalkyleneimine and a substituted alkyl trialkyl quaternary ammoniumsalt of formula (I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with a hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl; wherein the polyamine has formula (II):

wherein n is an integer from 0 to 100; each R₆ is independently C₂-C₆alkylene; and each R₇ is independently hydrogen or —R₆—NH₂,—R₆—NH—R₆—NH₂, or —R₆—N—(R₆—NH₂)₂; or (ii) the cationic polymer salt hasthe formula (III):

wherein each R₆ is independently C₂-C₆ alkylene; each R₇ isindependently hydrogen, —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or—R₆—N—(R₆—N(R₈)₂)₂; each R₈ is independently hydrogen or

each R₉ is independently C₂-C₆ alkylene substituted with hydroxyl or−OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; and each R₁₃ is independently C₁-C₆ alkyl.
 3. The method ofclaim 2, wherein the surface is part of a wellbore or equipment used inthe production, transportation, storage, and/or separation of the fluid.4. The method of claim 2, wherein the surface is part of equipment usedin a coal-fired process, a waste-water process, a farm, a slaughterhouse, a land-fill, a municipality waste-water plant, a coking coalprocess, or a biofuel process.
 5. The method of claim 3, wherein theequipment comprises a pipeline, a storage vessel, downhole injectiontubing, a flow line, or an injection line.
 6. The method of claim 2,wherein the fluid comprises natural gas or a liquid hydrocarbon.
 7. Themethod of claim 6, wherein the liquid hydrocarbon comprises crude oil,heavy oil, processed residual oil, bituminous oil, cocker oil, gas oil,fluid catalytic cracker feed or slurry, naphtha, diesel fuel, fuel oil,jet fuel, gasoline, or kerosene.
 8. A method for controlling microbes inprocess water, comprising: adding a composition to the process water,wherein the composition comprises a cationic polymer of formula (III):

wherein each R₆ is independently C₂-C₆ alkylene; each R₇ isindependently hydrogen, —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂, or—R₆—N—(R₆—N(R₈)₂)₂; each R₈ is independently hydrogen or

each R₉ is independently C₂-C₆ alkylene substituted with hydroxyl or—OR₁₃; R₁₀, R₁₁, and R₁₂ are each independently C₁-C₂₂ alkyl or C₇-C₂₂arylalkyl; R₁₃ is C₁-C₆ alkyl; n is an integer from 1 to 100; and eachX⁻ is independently an anion.
 9. A method of controlling microbes on asurface, comprising: adding a composition comprising a cationic polymersalt to the surface, wherein the cationic polymer salt comprises areaction product derived from a reaction of a polyamine or apolyalkyleneimine and a substituted alkyl trialkyl quaternary ammoniumsalt of formula (I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with a hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl; wherein any one of the following: (A) the cationic polymer salthas no substitutions within its main chain, no alkyl-quaternizedammonium within its main chain, and comprises at least 4 quaternaryammonium groups; or (B) the cationic polymer salt has one or moreterminal tertiary amine groups having the formula (IV):

wherein R₁₁ is R₁ without the X⁻ end group, and either: the polymer salthas no substitutions within its main chain or at least 1 of R₂, R₃, andR₄ is a C₉-C₂₂ alkyl group; or (C) R₂ and R₃ are C₆-C₂₂ alkyl or C₇-C₂₂arylalkyl and R₄ is methyl.
 10. The method of claim 8, wherein R₆ is aC₂ alkylene; R₇ is independently —R₈, —R₆—N(R₈)₂, —R₆—N(R₈)—R₆—N(R₈)₂,or —R₆—N—(R₆—N(R₈)₂)₂; and R₈ is


11. The method of claim 8, wherein the composition is added to theprocess water used in an industrial process selected from the groupconsisting of cooling water system, boiler water system, petroleumwells, downhole formations, geothermal wells, mineral washing, flotationand benefaction, papermaking, gas scrubbers, air washers, continuouscasting processes in the metallurgical industry, air conditioning andrefrigeration, water reclamation, water purification, membranefiltration, food processing, clarifiers, municipal sewage treatment,municipal water treatment, and potable water system.
 12. The method ofclaim 8, further comprising: contacting a spore or a thermophile in theprocess water with the composition.
 13. The method of claim 8, furthercomprising: contacting a bacterium in the process water with thecomposition.
 14. The method of claim 8, wherein the cationic polymer isselected from the group consisting of

and any combination thereof.
 15. The method of claim 8, wherein thecationic polymer is added to the process water to an amount ranging fromabout 1 ppm to about 1000 ppm.
 16. The method of claim 8, wherein thecomposition further comprises a biocide selected from the groupconsisting of chlorine, hypochlorite, ClO₂, bromine, ozone, hydrogenperoxide, peracetic acid, peroxysulphate, glutaraldehyde,dibromonitrilopropionamide, isothiazolone, terbutylazine, polymericbiguanide, methylene bisthiocyanate, tetrakis hydroxymethyl phosphoniumsulphate, and any combination thereof.
 17. The method of claim 8,wherein the composition further comprises a carrier.
 18. The method ofclaim 17, wherein the carrier comprises water, an alcohol, an aromatichydrocarbon, an alkylene glycol, an alkyleneglycol alkyl ether, or acombination thereof.
 19. A method for controlling microbes in an aqueoussystem, comprising adding to the aqueous system a reaction productderived from a reaction of a polyamine or a polyalkyleneimine and asubstituted alkyl trialkyl quaternary ammonium salt of formula (I):

wherein each X⁻ is independently an anion; R₁ is C₁-C₆ alkylenesubstituted with a hydroxyl or —OR₅ and an X⁻ end group; R₂, R₃, and R₄are each independently C₁-C₂₂ alkyl or C₇-C₂₂ arylalkyl; and R₅ is C₁-C₆alkyl.
 20. The method of claim 19, wherein any one of the following: (A)the cationic polymer salt has no substitutions within its main chain, noalkyl-quaternized ammonium within its main chain, and comprises at least4 quaternary ammonium groups; or (B) the cationic polymer salt has oneor more terminal tertiary amine groups having the formula (IV):

wherein R₁₁ is R₁ without the X⁻ end group, and either: the polymer salthas no substitutions within its main chain or at least 1 of R₂, R₃, andR₄ is a C₉-C₂₂ alkyl group; or (C) R₂ and R₃ are C₆-C₂₂ alkyl or C₇-C₂₂arylalkyl and R₄ is methyl.